WO2012021157A1

WO2012021157A1 - Method for making hydrophobic organic fiber and particulate for sorbing liquid hydrocarbons

Info

Publication number: WO2012021157A1
Application number: PCT/US2011/001379
Authority: WO
Inventors: Charles Diamond
Original assignee: Charles Diamond
Priority date: 2010-08-09
Filing date: 2011-08-04
Publication date: 2012-02-16
Also published as: US20120032369A1

Abstract

Methods for making organic fibers for sorbing liquid hydrocarbon spills. The methods include the steps of obtaining unfiberized organic material that has been pretreated with a hydrophobic agent and fiberizing the pretreated unfiberized organic material such that the material is reduced in size to form an organic fiber particulate of a desired size. The fiberizing results in the hydrophobic agent coating all exposed surfaces of the organic fiber particulate to form a substantially hydrophobic organic fiber particulate without the addition of any additional hydrophobic agent.

Description

METHOD FOR MAKING HYDROPHOBIC ORGANIC FIBER AND PARTICULATE FOR SORBING LIQUID HYDROCARBONS

FIELD OF INVENTION

This patent relates to improved methods of making hydrophobic and/or hydrophobic and oleophyllic organic fibers including cellulose fiber particulate for sorbing liquid hydrocarbon spills on land and/or on water, hereinafter referred to as the "Methods of the present invention."

BACKGROUND OF THE INVENTION

Organic fibers are well known for their superior absorbent properties for both water based and oil based liquids (including paints and liquid hydrocarbons). This presents a problem in many absorbent applications such as when the objective is to selectively remove only the oil from oil spills on water or to filter or separate oil from oil and water. To achieve the objective of a selective oil-only sorbent it is desirable to treat the fibers to reject water while retaining or enhancing their oil absorbent properties.

The methods for conditioning organic particulate and/or fibers to improve and impart hydrophobic and oleophyllic properties for their use as oil-only sorbents, disclosed in the prior art and literature fall into three distinct categories.

The first category involves applying a hydrophobic agent in which the particulate and/or fibers are conditioned to achieve the desired levels of hydrophobic and oleophyllic properties. The conditioning methods taught in this prior art are spraying, aeration and wetting. The disadvantage with this method is the lack of uniform application of the hydrophobic and oleophyllic agent to dry aerated particulate, as disclosed in the various patented hopper/blender arrangements and spraying techniques. The disadvantages with methods involving a wetted slurry are the additional energy, time and machinery required. A further disadvantage is the additional step for drying the particulate once the hydrophobic and/or oleophyllic agent has been applied. A number of patents disclose methods and systems falling within this category.

U.S. Patent Number 5,582,644 discloses a system for coating discontinuous fibers with a liquid coating material with a hopper/blender which entrains the fiber particles in a toroidal mass of moving fibers.

U.S. Patent Number 5,352,780 discloses a method for making cellulose flakes and pellets and for applying a hydrophobic agent to the pieces.

U.S. Patent Number 5,064,689 discloses a method of treating discontinuous fibers whereby the discontinuous fibers are entrained in a gaseous medium and coated while entrained with a substantially continuous coating of a binder material. This method is said to be used to impart hydrophobic and oleophilic properties to cellulose fibers.

U.S. Patent Number 4,537,877 discloses a particulate oil-absorbing composition having hydrophobic cellulose pulp fibers and inorganic filler. Possible additives are retention agents, wax, latex, sizing, resin polymers, or prepolymers.

U.S. Patent Number 3,770,575 discloses a method for making a hydrophobic fibrous material wherein a wet pulp is treated with conventional chemical sizing materials, and thereafter the pulp is flash dried. The sized, flash-dried hydrophobic fibrous material may be used to sorb oil from the surface of water.

The second category involves the application of hydrophobic agents to organic fibers. Such methods include enclosing organic fibers in a liquid-permeable hydrophobic shell, which method has the disadvantages of the additional step of putting the organic materials into a shell, and the inability to use the material in a loose form that is hydrophobic. A number of patents disclose methods and systems falling within this category. U.S. Patent Number 5,834,385 discloses an absorbent article for use in cleaning oil spills, which includes a first-exposed outer layer of hydrophobic, liquid-permeable, fibrous polymeric non-woven web, and an absorbent body within the outer layer, comprising oil- absorbent, cellulose-based material. The absorbent article selectively absorbs oil because the outer hydrophobic layer repels water but attracts oil and transfers the oil to the oil absorbent body encased within the exposed outer layer.

U.S. Patent Number 5,186,831 discloses a product for sorbing oil including an absorbent fiber core encapsulated in an adsorbent sheet, the adsorbent sheet being oleophilic, substantially hydrophobic, and capable of passing oil there-through to the absorbent core.

The third category involves heat treating specific cellulose substrates. This category has the disadvantage of requiring a costly heating step, and further is restricted to treating specific substrates such as: wood, reject fibers from the chemical pulping of wood, and high yield wood pulp which has ether extractives. A number of patents disclose methods and systems falling within this category.

U.S. Patent Number 5,1 10,785 discloses a composition of matter which is prepared by subjecting wood-like particles such as sawdust to a treatment wherein the particles are subjected to selectively controlled thermolytic heating to cause the hemicellulose to be converted to an oil-like oleophilic and hydrophobic substance on the cell walls and to reduce the thickness of the cell walls to render the particles oleophilic and hydrophobic for use as an oil absorbent.

U.S. Patent Number 4,670,156 discloses a hydrophobic sorbent which is made by subjecting fibrous starting material, consisting essentially of a member selected from the group consisting of reject fibers obtained from the chemical pulping of wood according to a sulphite process, reject fibers obtained from the chemical pulping of wood according to a sulphate process, and mixtures thereof, to rapid heating at a temperature sufficient to expand the fibers through gasification of the moisture therein.

U.S. Patent Number 4,343,680 discloses the treatment of high yield wood pulp which has ether extractives of greater than about 3.0% at temperatures of about 105°C or higher for at least 16 hours followed by fluffing of the heat treated pulp resulting in a oil absorbent that is both hydrophobic and oleophilic.

As is clear from the foregoing, there is a need for a method of making organic fiber based hydrophobic oil sorbents that avoids the difficulties of applying a hydrophobic agent uniformly to organic fibers and particulate, without wetting then drying the material, without sacrificing function as a loose material, and without needing to heat the material or restrict the input stream to wood-like material. Such a solution is not found in the prior art because the hydrophobic agent is inherently difficult to apply uniformly to organic fibers and particulate due to the complex surface matrix of organic fibers, which is necessary for trapping sorbed liquid hydrocarbons.

SUMMARY OF THE INVENTION

The present invention includes several methods of making hydrophobic organic fibers and particulate in which the organic fiber material has been pretreated with a hydrophobic agent prior to fiberizing. In the first and second methods of the present invention, the pretreated unfiberized organic material is subsequently fiberized into a hydrophobic organic fiber particulate that is suitable for sorbing liquid hydrocarbons, both on land and on water, and/or filtering or separating oil from mixtures of oil and water. In the third method of the present invention, the pretreated unfiberized organic material is subsequently sliced or shredded. For purposes of this patent, the term "organic fiber particulate" refers to organic fibers, organic particulates and/or combinations of organic fibers and particulates, and the term "unfiberized organic material" refers to organic materials having a size greater than one inch in any dimension.

The methods of the present invention differ substantially from the methods currently used insofar as the unfiberized material was pretreated with a hydrophobic agent before it is fiberized or otherwise broken down, instead of attempting to uniformly coat fibers and/or particulate. The pretreatment of the unfiberized material with a hydrophobic agent prior to fiberizing is counterintuitive and contrary to current practice, as it would appear that the subsequent fiberization process would expose untreated portions of the core of the material that would allow water to be absorbed by the fibers and/or particulate. However, the inventor of the present invention has discovered that the rubbing action and naturally elevated temperature of the hydrophobic organic fibers created by the fiberization process results in a softening and natural disbursal of the formerly hardened hydrophobic material onto the exposed untreated portions of the unfiberized material. Thus, even though the unfiberized material may not be fully saturated such that it contains untreated portions before it is fiberized, the fibers and particulate produced from the unfiberized material exhibit a substantially uniform hydrophobic coating about each of their exposed surfaces without the addition of any hydrophobic agents to the fiberized material.

In their most basic form, each of the first and second methods of the present invention include the steps of obtaining an unfiberized organic material that has been pretreated with a hydrophobic agent and fiberizing the pretreated material such that the pretreated material is reduced in size to form an organic fiber particulate of a desired size and in which the hydrophobic agent coats all exposed surfaces of the organic fiber particulate to form a substantially hydrophobic organic fiber particulate.

It is preferred that the organic material is at least one of a group consisting of cardboard, corrugated cardboard, paper, paperboard, formed cellulose, and molded cellulose, and the hydrophobic agent is at least one of wax, rosin, starch, casein, whey, soya protein, natural resin, synthetic resin, water-insoluble polyvinyl alcohol, hydroxyethyl cellulose, ethyl cellulose, carboxymethyl cellulose, polyethylene, polypropylene, polyacrylate, and polyester.

In the first method of the present invention, no additional hydrophobic agent beyond that with which the unfiberized organic material has been pretreated is added during fiberization.

In a preferred embodiment of the first method of the present invention, the fiberizing step includes the steps of disposing the pretreated material into a shredder and shredding the pretreated material into fiber particles of an intermediate size. This embodiment preferably also then includes the step of removing any metallic objects from the shredded pretreated material, transferring the shredded pretreated material to a hammer mill having a desired screen size, hammer milling the shredded pretreated material into the organic fiber particulate of a desired size, moving the organic fiber particulate into an air filter, and separating the organic fiber particulate from the air stream. The term "air filter" includes air filters, cyclones, or any other agitating mechanism using air pressure.

In another embodiment of the first method, the fiberizing step includes the steps of disposing the pretreated material into a cutter or slicer, collectively referred to as slicer, and slicing the pretreated material until it forms strips having a width of between 1/32 inches and 1 inch, where the hydrophobic agent coats all exposed surfaces of the organic fiber to form a substantially hydrophobic organic fiber particulate. The preferred particles are strips of between 1/32 inches wide by 60 inches long and, more preferably, 1/8 inch wide by 12 inches long.

In another preferred embodiment of the first method, the step of obtaining an unfiberized organic material that has been pretreated with a hydrophobic agent involves obtaining waxed paper and/or waxed cardboard, collectively referred to as "waxed paper material," such as those commonly used in the food industry. In some such embodiments, the method includes the additional steps of cleaning and drying the waxed paper material prior to the fiberizing step.

In the second method of the present invention, the fiberizing step includes the steps of disposing the pretreated material into a shredder, shredding the pretreated materials into fiber particles of an intermediate size, transferring the shredded pretreated material to a hammer mill having a desired screen size, adding untreated organic fibers to the pretreated material, and hammer milling the pretreated material and untreated organic fibers into the organic fiber particulate of a desired size , such that the hydrophobic agent on the pretreated material coats all exposed surfaces of the organic fiber particulate to form a substantially hydrophobic organic fiber particulate. In a preferred embodiment, the untreated organic fibers are at least one of a group consisting of animal fibers and vegetable fibers.

The third method of the present invention includes the step of obtaining an unfiberized organic material that has been pretreated with a hydrophobic agent, but does not include the fiberizing step. Instead, the third method produces a finished product from slicing or shredding, as described above, alone. The inventor has found that it is not always necessary to completely fiberize the pretreated material: Sufficient dissemination of the hydrophobic agent across all exposed surfaces of the material may be achieved from slicing or shredding the pretreated unfiberized organic material alone, without complete fiberization.

In preferred embodiments of the third method, the finished product is packaged bulk in bales, in bags, and in all the standard configurations commonly used for sorbent materials. Such standard configurations for packaging include booms, pillows, socks, bilge skimmers, pads, blankets, boxes, jars, spill kits, drum protectors, mops, and other containers suitable for packaging fibrous materials. Each of these standard configurations is included in the third method's "packaging" step.

With the invention described herein, uniformly hydrophobic particulate is achieved with an improved method that is both simple and inexpensive. The improved methods circumvent the need for aerating then spraying the cellulose particulate. There is also no need for wetting or heating the cellulose particulate. Further, the input stream for the improved methods is not restricted to wood-like materials.

The improved methods have the advantage of avoiding the difficulties imposed by the convoluted outer surface matrix of organic fibers on the process of applying the hydrophobic agent to the outer surface. The invention thereby enables the cellulose particle size and shape to be optimized to maximize the sorptive capacity, resulting in a sorbent that is uniquely effective and less costly to produce than taught by any prior art.

The foregoing aspects of the invention are not meant to be exclusive and other features, aspects, and advantages of the present invention will be readily apparent to those of ordinary skill in the art when read in conjunction with the following description and accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flowchart showing the common steps of the methods of the present invention and how they differ.

FIG. 2 is a flowchart showing the steps of a preferred embodiment of the first method of the present invention in which utilized shredder is used.

FIG. 3 is a flowchart showing the steps of another preferred embodiment of the first method of the present invention in which a slicer is used.

FIG. 4 is a flowchart showing the steps of another preferred embodiment of the first method of the present invention in which waxed paper material is used.

FIG. 5 is a flowchart showing the steps of the second method of the present invention.

FIG. 6 is a flowchart showing the steps of the third method of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention includes methods of making hydrophobic organic fibers and particulate in which the organic material has been pretreated with a hydrophobic agent prior to fiberizing. The pretreated organic material is subsequently particulated into a hydrophobic organic fiber particulate suitable for sorbing liquid hydrocarbons, both on land and on water, and/or to filter or separate oil from oil and water. As shown in FIG. 1 , both first method 50 and second method 52 include the steps of obtaining an unfiberized organic material that has been pretreated with a hydrophobic agent 12 and fiberizing the pretreated material such that pretreated material is reduced in size to form an organic fiber particulate of a desired size and in which the hydrophobic agent coats all exposed surfaces of the organic fiber particulate to form a substantially hydrophobic organic fiber particulate 14. First method 50 and second method 52 differ in that no additional hydrophobic agent is added 16 in first method 50, and untreated organic fibers are added 18 in second method 52. The untreated organic fibers that are added in second method 52 may or may not be hydrophobic.

As described with reference to FIG. 2, in a preferred embodiment of first method

50, the fiberizing step 14 includes the steps of disposing the pretreated unfiberized organic material into a shredder 20; shredding the pretreated unfiberized organic material 22; removing any metallic objects from the shredded pretreated unfiberized organic material 24; transferring the shredded pretreated unfiberized organic material to a hammer mill having a desired screen size 26; hammer milling the shredded pretreated unfiberized organic material into the organic fiber particulate of a desired size 28; moving the orgnic fiber particulate into an air filter by allowing the organic fiber particulate to be drawn through a fiberizing and particulating machine 30; and separating the organic fiber particulate from an air stream created by the air filter 32.

A small production line will typically include a belt feed that brings the material into a shredder 20 where the material is typically brought to a size 22 of less than four inches in diameter, averaging from one half-inch to three inches in diameter. This size is the intermediate size. By reducing the material diameter at the first stage to under one half-inch it facilitates easy removal all the staples 24 as the under half-inch material moves through duct work, past powerful magnets that capture the loose metal on the way to the next stage, where the material size is reduced further where it is either fiberized and/or particulated to the desired finished size.

The second stage is preferably a hammer mill with a screen size 28 that is in the size range of 1/32 inch to one inch. This size is the desired screen size. The air filter, which may be an air blower, cyclone, or other similar air agitator, is usually placed after the hammer mill and often as a part of the hammer mill that is used to dry the material by air into and through the first stage shredder, past the magnets, into the hammer mill, through the sizing screen, then is blown into a cyclone 30 where the fibers are separated from the air stream 32. A very effective size for the best fiberizing has been found to be more typically in the range of 1/8 of an inch to 3/8 of an inch.

If a tub grinder or top loaded grinder is employed in the first stage of sufficient power, it is possible to achieve the desired finished fiber size in only one stage. After the fibers and/or particulate are completed they can be bagged or baled in a process that is separate or integral with the manufacturing line.

Now referring to FIG. 3, a second preferred embodiment of first method 50 is shown. In this embodiment, fiberizing 14 is achieved by disposing the pretreated unfiberized organic material into a sheer or cutter 34 and slicing the pretreated unfiberized organic material into strips of organic fiber particulate of a desired size 36, where the hydrophobic agent coats all exposed surfaces of the organic fiber to form a strip of substantially hydrophobic organic fiber particulate. The strips have a width of between 1/32 inches and 1 inch and a length of between 1/32 inches and 60 inches, and the preferred strips are preferably 1/8 inch wide by 12 inches long.

Now referring to FIG. 4, a third preferred embodiment of first method 50 is shown. In the case of waxed paper materials, this leaves only the one minimum step of fiberizing 14 to achieve the finished product. As shown in FIG. 4, however, the step of cleaning and drying the waxed paper material 40 may be performed prior to fiberizing 14. Waxed paper materials are a common waste of the food industry typically used to package fish, meat, poultry, vegetables, fruit, and liquids such as milk and juices then disposed of for lack of a recycling use. These materials have already fulfilled an important need, as typically the very lowest cost hydrophobic material to service the food and processed food industry. As a waste, these waxed materials are even lower in cost yet have all the desirable characteristics of a high performance oil absorbent. The wax and many other hydrophobic pretreatments also impart the further advantage of making the resulting organic fibers oleophyllic. Thus the waxed materials need only to be fiberized to produce fibers that are both hydrophobic and oleophyllic. The resulting fibers are very high performance oil only sorbent at a cost that is lower than any currently known alternative.

Typical of such pretreated organic materials that are waxed paper materials are: waxed paper, waxed cardboard, waxed corrugated cardboard such as of the group: wax impregnated cardboard or paper, spray coated cardboard or paper, dipped cardboard or paper, sheet coated cardboard or paper, and the like. A plentiful supply of the preferred pretreated cellulose materials is available in the waste stream. These waste materials are typically without a recycling path and are in abundant supply at a very low cost compared to the other forms of cardboard waste or paper waste.

Examples of such waste are: waxed corrugated cardboard boxes used for packaging and shipping of food products and the like, waxed paper scrap, waxed cardboard scrap and the like. The material size includes pretreated hydrophobic boxes and papers of every size up to the available size of the opening in the fiberizing machinery, (if necessary any oversize box can be broken down into smaller size, and no box would ever be too small). It is common for the hydrophobic organic material to arrive in bales. For example, full size boxes, cartons, parts of cartons, and papers can be received in bales where the entire bale of hydrophobic pretreated material is dropped into a tub grinder. The percentage of hydrophobic additive that exists in the pretreated hydrophobic material can be in the range of from 5% to 95% existing hydrophobic additive to substrate base material by weight.

In each of these preferred embodiments of first method 50, the pretreated organic hydrophobic material can be fiberized or particulated with a single machine or combination of machines such as grinders, shredders, choppers, sheers, cutters, pin mills, fiberizers, refiners, pulverizers, hammer mills and the like. The result is a hydrophobic organic fiber particulate that is also oleophilic and ideally suited for sorbing liquid hydrocarbons both on land and on water or to filter or separate oil from oil and water. The finished fiber and/or particle size can range from l/32nd of an inch to one inch as dictated by the optimum density characteristic that is desired in the finished product. For example a small particle size will have a higher absorption ratio but is more likely to be blown around by the wind if used where the air is turbulent, whereas a larger particle size can be more suitable for use under turbulent air conditions.

Now referring to FIG. 5, second method 52 of the present invention is shown, in which untreated organic fibers are added 18. The fiberizing 14 step of second method 52 includes the steps of disposing the pretreated unfiberized organic material to a shredder 42; shredding the pretreated unfiberized organic material into fiber particles of an intermediate size 44; adding untreated organic fibers to the fiber particles of an intermediate size 18; and hammer milling a combination of the fiber particles of an intermediate size and the untreated organic fibers into the organic fiber particulate of a desired size 46.

The untreated unfiberized organic materials may be made from cellulose and include cardboard, corrugated cardboard, paper, paperboard, formed cellulose, molded cellulose and the like. They may also be unfiberized organic materials made from organic fibers, including those that are animal based, vegetable based, and combinations of both. Materials made from animal based fibers include silk, hair (including; Alpaca, Angora, Bison Down, Camel hair, Cashmere, Catgut, Chiengora, Guanaco, Llama, Mohair, Pashmina, Qiviut, Rabbit, Silk, Sinew, Spider silk, Wool, Vicuna, Yak and combinations thereof that are often abundant in many parts of the world) wool, and feathers. Unfiberized organic materials made from vegetable based fibers, include those such as of the group: cotton, cardboard, bark, flax, hemp, jute, paper, (and also include Abaca, Bamboo, Coir, Kapok, Kenaf, Pina, Raffia palm, Ramie, Sisal, and combinations thereof that are often abundant in many parts of the world).

Now referring to FIG. 6, third method 54 of the present invention is shown. Third method 54, like first and second methods 50, 52, includes the step of obtaining an unfiberized organic material that has been pretreated with a hydrophobic agent 12, but unlike first and second methods 50, 52, does not include the fiberizing step 14. Instead, third method 54 produces a finished product from slicing 56 or shredding 58 the pretreated unfiberized organic material, as described above, alone. The inventor has found that it is not always necessary to completely fiberize the pretreated material: Sufficient dissemination of the hydrophobic agent across all exposed surfaces of the material may be achieved from slicing 56 or shredding 58 alone, without complete fiberization.

Preferred embodiments of third method 54 also include the step of packaging 60. The finished product is packaged bulk in bales, in bags, and in all the standard configurations commonly used for sorbent materials. Such standard configurations for packaging include booms, pillows, socks, bilge skimmers, pads, blankets, boxes, jars, spill kits, drum protectors, mops, and other containers suitable for packaging fibrous materials. Each of these standard configurations is included in the third method's "packaging" step 60.

The methods of the present invention produce a basic high performance hydrophobic and oleophilic low-cost fiber substrate that is also found able to impart its hydrophobic and oleophilic characteristics to other organic fibers that are either lacking hydrophobic and oleophilic characteristics or otherwise have minimal hydrophobic and oleophilic properties. Some of these organic fibers are exceedingly low in cost and as such would be desirable to be included as a substrate that would possess hydrophobic and/or hydrophobic and oleophilic properties. It has been found that from 5% to 90% of low performance organic fibers by weight relative to the pretreated hydrophobic material, can be introduced into the manufacturing process with benefits when introduced anywhere before the final fiberizing and pulverizing stage. The benefits are as follows: When low performance organic fibers are introduced before the final fiberizing or pulverizing stage there is a smearing effect and rubbing effect and heating effect from friction, that takes place that imparts the hydrophobic characteristic to the lower performance fibers that are introduced into the manufacturing stream.

One great advantage of the methods of the present invention is that no additional hydrophobic and/or oleophilic additives have been found necessary to achieve the resulting improvement in the hydrophobic and/or oleophilic properties other than merely starting with pretreated hydrophobic materials and the associated discovery that organic fibers lacking hydrophobic properties or having lower performance hydrophobic properties can be added and have been found to have been imparted with significant hydrophobic and/or hydrophobic and oleophilic characteristics. Thus, as shown in FIG. 5, in some embodiments of the invention, additional untreated fiber materials are added to the pretreated material during manufacturing.

Regardless of which embodiment of the methods is used to manufacture the hydrophobic organic fiber particulate, the resulting particulate may be further treated using the methods disclosed in the inventor's issued United States Patent No. 5,492,881 , which is incorporated herein by reference in its entirety.

The hydrophobic organic fiber particulate ("Material") produced by the methods of the present invention has broad use for emergency/remedial response, industrial use and consumer use. The emergency/remedial uses allow the Material to be used for oil spills on land and water. The industrial uses allow the Material to be on hand for all containment and mitigation of the ever present risk of mishandled liquid hydrocarbons. Consumers are in need of a clean, safe, and inexpensive process of dealing with undesired oil and its disposal.

The Material floats on water thereby providing a valuable use in the distribution of the Material both above and below the water in that it rises through liquid hydrocarbon contaminated water collecting and absorbing the oil as it migrates to the surface. On the surface, the Material floats allowing easy retrieval and recovery of the contaminant. Since the Material is hydrophobic, the water is released and not sorbed as the liquid hydrocarbon contaminated soaked Material is removed from the water. Once removed, the Material can be pressed to extract the oil for further use with the residual spent Material available to be used as a heating fuel or to be disposed of through land farming and/or bioremediation and/or carbon negative low temperature pyrolysis to capture the available energy and provide benefits to the environment without harm to the environment. The lower than water density of the Material, even when exposed to oil, allows the Material to be mixed with liquid hydrocarbon contaminated soils and agitated with water to allow for the removal of oil from soils.

Industries or persons that handle, produce, supply, use or sell liquid hydrocarbons would benefit from having the fiberized material "on hand" to respond to mishandling. The material can be used either in loose or packaged configurations to respond to liquid hydrocarbons that are improperly handled.

The finished product can be packaged bulk in bales, in bags, and in all the standard configurations commonly used for sorbent materials. Such standard configurations for packaging include booms, pillows, socks, bilge skimmers, pads, blankets, boxes, jars, spill kits, drum protectors, mops, and other containers suitable for packaging fibrous materials.

Two novel containments include packaging in a bun shaped like a hot dog bun or hamburger bun suitable for wiping a dipstick. Such a containment could be mounted under the hood of an automotive vehicle or near an engine where it would be available as needed for wiping a dipstick prior to checking oil levels and could be referred to as a "Dipstick Bun." Another novel containment would be inside an oil drain pan, can, or box, which would have the advantage when draining oil from a vehicle or capturing cooking oil in a kitchen or when disposing of used oil in a work area, of converting that oil into a solid waste thereby allowing the oil to be disposed of as a solid waste in a land fill instead of as a hazardous waste, as is commonly distinguished by federal, state and municipal rules and regulations.

The methods of the present invention produce a high performance hydrophobic and oleophyllic organic material suitable for sorbing liquid hydrocarbon spills outdoors and indoors on wet or dry surfaces such as land, snow, ice, and water. The significant performance improvement allows for a material that can be deployed above or below the surface of water indoors or outdoors. The high performance organic fibers prepared in this manner are found to retain their effectiveness in all weather conditions. Due to their low cost and high pickup ratio, (in excess of 30: 1 by weight), they are able to pick up spilled liquid hydrocarbons at a cost that is often far below the value of the retrieved liquid hydrocarbons.

With the methods of the present invention, the materials often have such a high percentage of hydrophobic agent that the rubbing action and naturally elevated temperature of the hydrophobic organic fibers during the manufacturing process are found to be able to impart their hydrophobic characteristic to other organic fibers that are otherwise lacking hydrophobic properties or have lesser hydrophobic and/or oleophilic properties that can be readily improved by their introduction into the manufacturing process before the final stage.

The methods of the present invention has been found to vastly improve the hydrophobic properties of virtually all organic fibers that are introduced together with the pretreated hydrophobic materials.

The methods of the present invention may be used as stand alone methods without any other materials or additives or in combination with other sorbent materials and additives such as inks and dyes, for color coding, fire retardants, for safety, oil-digesting microbes and nutrients for bioremediation, and solids that function as traction-restoring grit when used on land.

The resulting high performance, oil-only, organic fiber sorbents can be used as the active sorbing component inside sorbent booms, pads, pillows, blankets and the like. It may also be used in a loose form to remediate liquid hydrocarbon spills by utilizing a variety of deployment options such as dropping, blowing, throwing, bombing, bubbling, infusing, plowing or dumping the hydrophobic cellulose particulate onto, into or under the spill. It may also be used for oil-water separation.

Once the hydrophobic cellulose particulate has been used to sorb hydrocarbons, it may be squeezed to recover up to 98% of the sorbed liquid and/or burned for 100% recovery of the available energy, leaving less than 1% ash. The used particulate may also be used in combination with bioremediation technology or as a soil additive suitable for land farming techniques. An even more beneficial use for the used particulate is to apply low temperature pyrolysis, to remove the carbon, resulting in a non-polluting carbon negative hydrogen based fuel. The removed carbon is then available for use as a soil amendment that boosts agricultural yields 200% to 400%. The precipitated carbon has a porous structure ideally suited as a host for the indigenous anaerobic microbes common to the soil. These anaerobic microbes breathe in carbon dioxide and exhales oxygen helping to reduce Global Warming while reducing atmospheric pollution and preserving fossil fuels.

The methods of the present invention allow the organic fibers' size and shape to be optimized to achieve the highest possible sorptive capacity making a sorbent that is both highly effective and inexpensive to produce.

The methods of the present invention produce a robust oil-only sorbent that is also highly versatile in its many applications and formulations in combination with other products and additives.

The methods of the present invention produce a sorbent that can be biodegraded, is non-toxic and can be manufactured entirely from materials in the waste stream that otherwise end up in our landfills. In conclusion, the present invention provides methods of making a variety of hydrophobic organic fibers and particulates of exceptionally high performance at a very low cost that exceeds all the prior art, whereby the disadvantages of the prior art are resolved and avoided, wherein specific advantages over the prior art are achieved. Those skilled in the art of treating organic fibers have long considered the problem of imparting hydrophobic agents to organic fibers. None, however, recognized the advantages of fiberizing or particulating a pretreated hydrophobic organic fiber material. The method of the present invention provides a uniform application of the hydrophobic agent without the added steps, difficulty, and cost associated with any of the prior art.

Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions would be readily apparent to those of ordinary skill in the art. Therefore, the spirit and scope of the present invention should not be limited to the description of the preferred versions contained herein.

Claims

We claim:

1. A method for making hydrophobic organic fibers for sorbing liquid hydrocarbon spills, said method comprising the steps of:

obtaining an unfiberized organic material that has been pretreated with a hydrophobic agent; and

fiberizing the pretreated unfiberized organic material such that the pretreated unfiberized organic material is reduced in size to form an organic fiber particulate of a desired size;

wherein the hydrophobic agent coats all exposed surfaces of the organic fiber particulate to form a substantially hydrophobic organic fiber particulate; and

wherein no additional hydrophobic agent is added.

2. The method as claimed in claim 1, wherein said step of fiberizing the pretreated unfiberized organic material comprises:

disposing the pretreated unfiberized organic material into a shredder; and shredding the pretreated unfiberized organic material into organic fiber particles of an intermediate size.

3. The method as claimed in claim 2, wherein said step of fiberizing the pretreated unfiberized organic material further comprises the step of removing any metallic objects from the shredded pretreated unfiberized organic material.

4. The method as claimed in claim 3, wherein said step of fiberizing the pretreated unfiberized organic material further comprises the steps of:

transferring the shredded pretreated unfiberized organic material to a hammer mill having a desired screen size; hammer milling the shredded pretreated unfiberized organic material into the organic fiber particulate of a desired size;

moving the organic fiber particulate into an air filter by allowing the organic fiber particulate to be drawn through a fiberizing and particulating machine; and

separating the organic fiber particulate from an air stream created by the air filter.

5. The method as claimed in claim 2, wherein said step of fiberizing the pretreated unfiberized organic material further comprises:

transferring the shredded pretreated unfiberized organic material to a hammer mill having a desired screen size;

hammer milling the shredded pretreated unfiberized organic material into the organic fiber particulate of a desired size;

6. The method as claimed in claim 1, wherein said step of fiberizing the pretreated unfiberized organic material comprises:

disposing the pretreated unfiberized organic material into a sheer; and

slicing the pretreated unfiberized organic material into organic fiber particulate of a desired size.

7. The method as claimed in claim 6, wherein said step of slicing the pretreated organic material into organic fiber particulate of a desired size comprises slicing the pretreated organic material into strips of organic fiber particulate having a width of between 1/32 inches and 1 inch and a length of between 1/32 inches and 60 inches.

8. The method as claimed in claim 7, wherein said step of slicing the pretreated organic material into organic fiber particulate of a desired size comprises slicing the pretreated organic material into strips of organic fiber particulate having a width of between 1/32 inches and 1 inch and a length of between 1/8 inches and 12 inches.

9. The method as claimed in claim 1 , wherein said step of obtaining an unfiberized organic material that has been pretreated with a hydrophobic agent comprises obtaining an amount of waxed paper material.

10. The method as claimed in claim 9, further comprising the steps of cleaning and drying the waxed paper material prior to said fiberizing step.

1 1. The method as claimed in claim 1, wherein said step of obtaining an unfiberized organic material that has been pretreated with a hydrophobic agent comprises obtaining at least one of a group of unfiberized organic materials consisting of cardboard, corrugated cardboard, paper, paperboard, formed cellulose, and molded cellulose, that has been pretreated with at least one of a group hydrophobic agents consisting of wax, rosin, starch, casein, whey, soya protein, natural resin, synthetic resin, water-insoluble polyvinyl alcohol, hydroxyethyl cellulose, ethyl cellulose, carboxymethyl cellulose, polyethylene, polypropylene, polyacrylate, and polyester.

12. A method for making hydrophobic organic fibers for sorbing liquid hydrocarbon spills, said method comprising the steps of:

fiberizing the pretreated unfiberized organic material such that the pretreated unfiberized organic material is reduced in size to form an organic fiber particulate of a desired size and such that the hydrophobic agent coats all exposed surfaces of the organic fiber particulate to form a substantially hydrophobic organic fiber particulate, wherein said fiberizing step comprises the steps of:

disposing the pretreated unfiberized organic material into a shredder;

shredding the pretreated unfiberized organic material into fiber particles of an intermediate size;

adding untreated organic fibers to the fiber particles of an intermediate size; and hammer milling a combination of the fiber particles of an intermediate size and the untreated organic fibers into the organic fiber particulate of a desired size.

13. The method as claimed in claim 12, wherein said step of adding untreated organic fibers comprises adding at least one of a group of untreated organic fibers consisting of animal fibers and vegetable fibers.

14. The method as claimed in claim 12, wherein said step of obtaining an unfiberized organic material that has been pretreated with a hydrophobic agent comprises obtaining at least one of a group of unfiberized organic materials consisting of cardboard, corrugated cardboard, paper, paperboard, formed cellulose, and molded cellulose, that has been pretreated with at least one of a group hydrophobic agents consisting of wax, rosin, starch, casein, whey, soya protein, natural resin, synthetic resin, water-insoluble polyvinyl alcohol, hydroxyethyl cellulose, ethyl cellulose, carboxymethyl cellulose, polyethylene, polypropylene, polyacrylate, and polyester.

15. A method for making a sorbent for sorbing liquid hydrocarbon spills, said method comprising the steps of:

obtaining an unfiberized organic material that has been pretreated with a hydrophobic agent;

disposing said pretreated unfiberized hydrophobic organic material into a sheer; slicing the pretreated unfiberized hydrophobic organic material until it forms strips having a desired size, wherein said slicing step causes the hydrophobic agent to coat all exposed surfaces of the strips of organic material to form substantially hydrophobic strips of organic material, and wherein no additional hydrophobic agent is added; and

disposing the substantially hydrophobic strips organic material into a containment.

16. The method as claimed in claim 15, wherein said step of slicing the pretreated unfiberized hydrophobic organic material into strips of hydrophobic organic material of a desired size comprises slicing the pretreated unfiberized hydrophobic organic material into strips having a width of between 1/32 inches and 1 inch and a length of between 1/32 inches and 60 inches.

17. The method as claimed in claim 16, wherein said step of slicing the pretreated unfiberized hydrophobic organic material into strips of hydrophobic organic material of a desired size comprises slicing the pretreated unfiberized hydrophobic organic material into strips having a width of between 1/32 inches and 1 inch and a length of between 1/8 inches and 12 inches.

18. The method as claimed in claim 15 wherein said containment is chosen from a group consisting of a boom, a pillow, a sock, a bilge skimmer, a pad, a blanket, a mops, and a dipstick bun.

19. The method as claimed in claim 15 wherein said containment is a dipstick bun.