WO2001010547A2

WO2001010547A2 - Material sorbent with respect to petroleum/oil or water soluble substances

Info

Publication number: WO2001010547A2
Application number: PCT/FR2000/002254
Authority: WO
Inventors: Wayne E. Shaw; Mark Trabbold; Kenneth D. Knapp
Original assignee: Saint-Gobain Isover
Priority date: 1999-08-05
Filing date: 2000-08-04
Publication date: 2001-02-15
Also published as: EP1144108A2; NO20011671D0; JP2004500231A; WO2001010547A3; AU6850600A; EP1144108A3; NO20011671L

Abstract

The invention concerns a sorbent material comprising a fibrous material which, in a first embodiment, comprises an oleophilic coating and, in a second embodiment, is associated with a particulate hydrophilic material. The invention also concerns methods for obtaining said materials and their uses.

Description

SORBENT MATERIAL FOR OIL / OILS OR FOR WATER-SOLUBLE POLLUTANTS

The present invention relates in general to sorbent materials and in particular, in a first variant, to oleophilic materials suitable for the absorption and / or adsorption of oils / oils, as well as to sorbent materials suitable for absorbing water (or solvent (s) in which pollutants are dissolved. Accidental discharges of crude and refined oils, petrol and similar products, especially in watercourses, have the potential to cause significant damage to the ecosystem. If a spill is large, local populations of mammals, aquatic organisms and other animals and plants can be at risk. Many of the techniques known for Eliminating or mitigating the impact of such spills can be costly and time-consuming, and their effectiveness may be poor and these techniques may be poor. do not cause secondary problems. The ignition of oil spills on water or on land can, for example, be dangerous for people or property as well as for surrounding animal and plant life. Petroleum dispersants and detergents often produce residual byproducts which can themselves be hazardous. Because of its inadequacies, sorbent materials often represent an attractive alternative for cleaning up oil or similar spills. As they are used here, terms such as "sorbent" and so on should be understood as including materials which "absorb" and / or "adsorb" liquids. In some cases, however, where appropriate for clarity of explanation, this text will specifically state whether phenomena involving "absorption capacity" or "absorption capacity" are present or if one over the other predominates.

Sorbent materials which have shown potential as an effective means of treating both aquatic and non-aquatic oil slicks include fibers and mineral and glass particles. US Patent No. 5,215,407, for example, proposes the use of blown wool compositions based on glass fibers, shredded or non-shredded, for the treatment of oil spills located on bodies of water or on land . This patent states that an advantage of using such materials on water is the fact that, if an appropriate glass fiber insulating material is used, the glass fiber exhibits a sorption affinity to vis-à-vis oil rather than vis-à-vis water. Due to the inorganic nature of glass fiber blowing insulating materials, such materials "adsorb" more than "absorb" liquids. The glass fiber compositions disclosed in Patent No. 5,215,407 consist essentially of glass fiber blowing insulators with the possible inclusion of cork and / or styrofoam to provide a capacity for absorption and compressive strength. Fiberglass can also be sprayed using a mist generated from an antifreeze and water solution, to reduce static electricity and the dust released when spraying particles on a spill of oil.

U.S. Patent No. 5,215,407 mentions several possible commercially available materials which are suitable for use as a base for the glass fiber blowing composition particles disclosed therein: InsulSafe III glass fiber blowing insulation ^® , manufactured by CertainTeed Corporation, of Valley Forge, Pennsylvania, Rich-R ^® glass fiber blowing insulation, manufactured by Johns Manville Corporation, of Denver, Colorado and Thermacube ^® glass fiber blowing insulation, manufactured by Owens company Corning, of Toledo, Ohio. For aquatic oil spill applications, the patent is said to recommend the use of InsulSafe III ^® glass fiber blowing insulation because it does not tend to absorb water. In relative terms, compared to Rich-R ^® and Thermacube ^® glass fiber blowing insulation, InsulSafe III ^® glass fiber blowing insulation can absorb less water. However, it is not a truly hydrophobic material.

InsulSafe III ^® glass fiber blowing insulation is an insulating glass fiber in bulk, with virgin, white fibers, unbound, applied using pneumatic means for the insulation of attics, wall surfaces and other building areas. To facilitate installation and improve the performance of the insulation in its specialized building insulation applications, glass fibers are coated with several materials designed to achieve certain results or certain beneficial properties. Among these are silicone emulsions which act as a lubricant and quaternary ammonium salts which act as an antistatic agent. Silicone is a protective coating on glass (i.e. it prevents abrasion of the fibers by mutual friction of one fiber on the other). The silicone improves recovery during the blowing process (i.e. restores resilience to the fiber to achieve a high R value).

InsulSafe III ^® glass fiber blowing insulation has been shown to be just like Thermacube ^® glass fiber blowing insulation (which is recognized in U.S. Patent No. 5,215,407 as being even more water-absorbent than InsulSafe III ^® glass fiber blowing insulation, sinks quickly when used to treat a layer of aquatic hydrocarbon. The sunken oil spill treatment material can, in some case, be difficult, if not impossible, to recover. This, in turn, can lead to ecological contamination of the marine environment in the vicinity of the sinking material.

US Patent No. 5,078,890 describes a technique for treating an aquatic oil spill by using felt particles made of mineral wool (glass wool or rock wool). The mineral wools are bound by a hydrophobic formophenolic binder resin and are cured at elevated temperature. The felts are cut into particles of less than 4 cm and are then compressed to reduce their volume during storage and transport. At the time of application, the densified particles are decompressed and unbound and are then sprayed on an oil spill by a pneumatic current, so that they return to their original density. Silicone or similar hydrophobic agents may be made available in addition to the binder resin at the time of manufacture of the felts in an amount of approximately 0.5 to 3.0 percent by weight of the glass fibers. The product described in American patent No. 5,078,890 is marketed by the company Saint-Gobain Isover, in France. It is oleophilic and hydrophobic and floats on water and is therefore useful for its future applications. Its manufacturing process and the subsequent handling and implementation techniques are, however, somewhat complicated as well as demanding from a material, energy and financial point of view.

Fiberglass has been proposed for use as a means of cleaning or absorbing accidental oil spills on land and water. U.S. Patent No. 5,078,890, as cited above, describes the use of a commercially available glass fiber insulator for such purposes. However, the coating materials applied to conventional glass fiber blowing wool insulation, which are useful additives when using glass fiber for its designated purpose as building insulation, do not compensate in a way Significantly the tendency of fiberglass to sink when the insulation is used to clean up aquatic oil spills. And US Patent No. 5,215,407 discloses a petroleum-based cleaning product based on glass fibers, which, although capable of floating, is nevertheless somewhat difficult to manufacture and use.

Figure 1 (prior art) illustrates a mass of conventional loose glass fiber blowing wool 10 (density = 2.55 g / cm ³ ) suspended above discrete amounts of water 12 (density = 1.0 g / cm ³ ) and of SAE quality motor oil 14 14 (density = 0.95 g / cm ³ ), placed on a solid substrate 16 before the contact of the glass fibers with the oil and the water.

FIG. 2 (prior art) shows the glass fiber 10 in contact with the substrate 16 and the adsorption of oil and water which are symbolized, respectively, by the ovals 12 and 14. FIG. 2 reflects the fact that conventional bulk glass fibers 10 exhibit excellent wicking characteristics both with respect to water and with respect to oil and indiscriminately adsorb both liquids . In fact, water is adsorbed faster than oil due to its lower viscosity.

FIG. 3 (prior art) shows a bundle or a mass of conventional glass fibers 10, submerged in a volume of water 12, placed in a container 18, shortly after the placement of the glass fibers on the surface of the water. Due to the excellent wicking properties of glass fibers, coupled with its density which is approximately 2 Vi greater than that of water, the mass quickly adsorbs its available capacity of water and sinks to the bottom of the container 18 .

FIG. 4 (prior art) describes a mass of CertainTeed InsulSafe NT 10 glass fiber blowing wool insulation shortly after adsorption of an amount of Brass River crude oil which had previously been spilled on an amount of water 12 in container 18. The fiberglass 10, however, quickly and indiscriminately adsorbs both water and petroleum (ovals 12, 14). Once the water 12 and the oil 14 penetrate and saturate the fiber matrix, the fiberglass sinks quickly. Therefore, there is a need for a hydrophobic and oleophilic sorbent material which is useful for treating aquatic and non-aquatic petroleum pollutants. The material should preferably exhibit high buoyancy when used in aquatic environments, and be comparatively inexpensive and easy to manufacture and use.

The present invention firstly relates, in a first variant, to a “sorbent” material comprising a fibrous material, in particular free fibers, which is at least partially coated with an oleophilic coating consisting, mainly, in particular, essentially silicone (s). It is defined more precisely in claims 1 to 8. The term “mainly” means an amount by weight of at least 50% of the coating, and by “essentially” an amount by weight of at least 80 to 90% of the coating . The invention also relates to the process for obtaining such a "sorbent" material, in particular defined in claims 9 and 11 and its applications defined in claim 12.

The invention in its first variant becomes easier to grasp from the following description of the preferred embodiments of the latter, illustrated, by way of example only, in the attached drawings, in which:

> Figure 1 is a view comparing the approximate densities of blowing wool of conventional bulk glass fibers, water and motor oil; FIG. 2 is a view describing the undifferentiated adsorption capacity of conventional bulk glass fibers with respect to oil and water; > - Figure 3 is a view of a quantity of conventional bulk glass fibers which have adsorbed water and which then sank in water;

> - Figure 4 is a view of a quantity of conventional bulk glass fibers which have indiscriminately adsorbed oil and water and which then sank in water; and - Figure 5 is a view of a first preferred embodiment of a sorbent material according to the first variant of the present invention, adsorbing the oil selectively with respect to water; ^• Figure 6 is a view of a first preferred embodiment of a sorbent material according to the first variant of the present invention which has selectively adsorbed the oil and continues to float on water. In the course of research and development leading to the present invention, as described below in more detail, it has been discovered that a coating consisting mainly (mainly) of silicone (s) should have the effect of floating mineral fiber insulation such as loose glass fibers in the event of contact with a body of water. However, InsulSafe III ^® glass fiber blowing insulation has been shown to darken quickly when placed in water. Although the reason for this behavior is not fully understood, it could be that the antistatic agent based on quaternary ammonium salts is in some way responsible for the substantial suppression of the buoyancy effect of silicone.

The present invention uses oleophilic and hydrophobic fibrous sorbent materials and methods for the manufacture and use of such materials. Sorbents are useful for removing oil slicks and similar discharges from rivers and land structures. In one embodiment, the fibrous materials include loose (i.e. unbound) mineral (glass) fibers, commonly known as "blown wool", "blowing wool" or "blowing wool", or fiber particles of glass. In another embodiment, the fibrous materials include free cellulosic fibers. The invention however includes fibers, whether mineral or cellulosic, which are linked, that is to say sheathed by a sizing composition (generally containing resins, based on phenolformaldehyde and urea in particular). According to the two embodiments, the fibrous materials are coated with a light coating of a substance which allows the fibrous materials to float in water and which therefore makes them easily recoverable when used for elimination of oil spills from water bodies. The coating substance consists mainly of silicone, but may also include other constituents, such as paraffin oil.

The sorbent materials according to the invention are easier to manufacture and use and have characteristics of sorption capacity and buoyancy comparable or superior to those of the fibrous petroleum sorbents known hitherto in the prior art. FIG. 5 qualitatively illustrates the characteristics of adsorption capacity of the blowing wool of loose glass fibers 110, in accordance with the present invention, as a function of discrete quantities of water 112 and SAE quality motor oil 30 114 (“SAE” means “Society of Automative Engineers”). Fiberglass 110 can be manufactured according to any process suitable for the production of loose glass fibers, for example, gas centrifugation and drawing techniques. Processes of this kind are well known to those skilled in the art. They will therefore not be discussed in detail here. After the glass fiber is formed, however, and in accordance with an exemplary embodiment of the present invention, the glass fiber is preferably coated using from about 0.05 to about 0.10 percent by weight of silicone based on the weight of the fiber.

If the silicone content is substantially less than about 0.05% by weight of silicone, the fibers do not retain their buoyancy. There is however no scientific limit indicating how much silicone can be used. The silicone has a specific weight of less than 1.0 grams / cm ³ . Given its natural buoyancy, 100% added silicone should also work. In practice, however, high levels of silicone would be wasteful and costly. The preferred range is between 0.05% and 0.5% of silicone.

With regard to the type of silicone that can be used, it is possible to choose, in particular, emulsions in the form of fluids having a viscosity of ten to a few hundred centistokes (for example between 50 and 400, preferably between 100 and 300 centistokes, in particular around 200 centistokes, their molecular mass can be between 1000 and 100,000, in particular 5000 to 15000. Preferably, these are silicones which are not reactive at room temperature, but when they are applied to hot fibers, especially when leaving centrifuges, silicone can advantageously tend to form irreversible chemical bonds with mineral fibers, in particular with glass fibers.

An example of silicone of interest to the invention is in particular PDMS (polydimethylsiloxane), of chemical formula:

CH3 I

R - [O-Si] • - O-R I CH3

with R radicals which may be alkyls of the methyl type or an alcohol function OH. Note also that different silicones are mixed in varying proportions. The properties of these silicones vary, in particular according to the type of radicals R (or if one or the other of methyl is substituted) which can be alkyl or unsaturated groups, by example of phenyl, propyl, substituted / branched alkyls. This choice of radicals attached to silicon makes it possible to modify the properties of silicon, in particular its degree of hydrophobicity.

The glass can be coated by the following method, for example: when the glass fibers leave a centrifuge basket (for example a unit for forming fibers by centrifugation), they are immediately subjected to spraying using the silicone emulsion (in aqueous phase). The silicone emulsion is pumped from a storage tank through a system of flexible pipes to a 0.5 inch (1.27 cm) stainless steel tubing, which has been made in the form of a circular ring having a diameter of approximately 36 inches (0.9 m). Several spray nozzles can be located around this ring. The spray nozzles are directed towards the center. When the fibers are formed, the pressurized air, introduced during the fiber formation, drives the fibers down and through this spray ring. The newly formed fibers are coated with the silicone emulsion as they pass through the ring at a very high speed.

The product according to the example preferably does not use any binding agent (for example a formphenol resin) and provides a hydrophobic, oleophilic, bulk product. Silicone is the only hydrophobic chemical constituent (several can be used as a mixture). The silicone creates a product which is hydrophobic and which, when blown, allows the fiber to relax after high compression. This product has many advantages compared to the products of the prior art, such as the bonded felt insulation having from 0.5 to 3.0% of silicone, described in American patent 5,078,890, to which reference has been made here. -above.

It has been observed that a silicone coating promotes the buoyancy of the glass fiber 110 while giving it oleophilic and hydrophobic characteristics. A preferred silicone is the product Dow Silicone 346 sold by the company Dow Chemical Company of Midland, Maryland. Since it is preferred to dispense glass fiber 110 pneumatically when used for the treatment of large oil spills, glass fiber 110 can optionally be coated with 1.0% 3.0% oil (s) in an amount sufficient to act as a dust suppressant, particularly during the flow phase of the fiberglass. The oil can be, for example, the oil "PROREX 100 ^® ", sold by the company Mobil Corporation or the product "SUNPAR LW110 ^® ", sold by the company Sun Company. Any oil or other substance suitable for suppressing dust, which does not have a material impact on the oleophilic and hydrophobic advantages conferred by silicone would, however, be acceptable from the point of view of the objectives of the present invention. A preferred composition includes 0.27% silicone and not more than 1.8% oil. As shown in Fig. 3, the glass fiber 110 preferably absorbs petroleum 114 rather than water 112.

An exemplary paraffin oil which can be added to prevent dust and irritation has a viscosity of between about 18.7 and 22.0 cSt at 40 ° C, a minimum flash point of 380 ° F, and a weight specific of about 0.862 at 60 ° F. Simulated oil slicks were made to compare the relative buoyancy characteristics of the conventional bulk glass fiber blowing wool insulation and the bulk silicone coated glass fiber blowing wool of the present invention. Each slick of oil was prepared in the laboratory by adding 15.0 grams of Brass River crude oil to 400.00 grams of tap water, kept in separate tanks at room temperature. 1.0 gram of CertainTeed InsulSafe III ^® shredded glass fiber blowing wool insulation was then placed in a container and 1.0 gram of loose silicone fiber blowing wool in accordance with the present invention, was placed in the other container. Within about a minute, each sample of glass fibers adsorbed substantially all of the petroleum. The CertainTeed InsulSafe III ^® glass fiber blowing wool insulation sample sank quickly. On the contrary, the sample of loose glass fiber blowing wool according to the present invention, the coating of which consists essentially of silicone, continued to float practically indefinitely.

FIG. 6 shows a mass of blowing wool of loose glass fibers, coated with silicone 110, in accordance with the present invention, floating on a volume of water 12 contained in the container 18. The glass fiber 110 adsorbs the petroleum (oval 14) with the substantial exclusion of water. In fact, in the event of deployment for the cleaning of aquatic oil spills, the fiberglass 110 is easily and completely recoverable, once saturated with oil. Consequently, the risk that the petroleum-soaked fibrous material will darken and possibly be lost to the bottom of a body of water is effectively eliminated.

In the course of the research and development which led to the present invention in its first variant, it has been observed that in addition to inorganic mineral fibers such as glass fiber blowing wool, a coating consisting essentially of silicone also improves the sorption capacity of loose and otherwise untreated (or bound) cellulosic fibrous materials. Untreated cellulose fibers, such as crushed newsprint, wood pulp and the like, both adsorb and absorb the liquid, while untreated fiberglass adsorbs water. However, like untreated fiberglass, untreated cellulosic fibers indiscriminately sorb water and oil. As a result, untreated cellulosic fibers, like untreated mineral fibers, tend to sink quickly when used for cleaning up oil spills. In accordance with the present invention, it has been observed that when cellulosic fibers are treated with a silicone which is the same or which is similar in quality and quantity to that applied to glass fiber 110 discussed above, the coated cellulosic fibers selectively adsorb and absorb petroleum at the expense of water. As a result, silicone coated cellulosic fibers exhibit significantly greater buoyancy compared to that of untreated cellulosic fibers. Specifically, the untreated cellulosic fibers tend to sink within a few minutes, while the silicone coated cellulosic fibers have been found to adsorb and absorb petroleum and continue to float for a period of between about 30 and about 60 minutes. According to either embodiment of the present invention, the silicone-coated fibrous materials which are made available here are sorbents effective against petroleum. In particular, silicone coated glass fiber 110 and cellulosic fibers have demonstrated a sorption capacity equal to more than 20 times, respectively more than 15 times, their own weight of SAE quality motor oil 30 .

Although the invention in its first variant has been described in terms of exemplary embodiments, it is not limited thereto. On the contrary, the appended claim should be understood in a broad sense, to include other variants and other embodiments of the invention which could be made by persons skilled in the art without departing from the scope and the scope of the invention.

Thus, in its first variant, the “loose” fibrous material, without sizing composition, is preferred. It has the advantage of being able to be blown. From an industrial standpoint, the step of spraying the sizing composition and the step of crosslinking it by passing the fibrous material through an oven are avoided. However, the invention also applies to bonded fibers. The emulsion containing the hydrophobic / oleophilic silicone (s) can be sprayed onto the fibers once glued by a spray crown placed below the crown used to spray the sizing, under the centrifuge plates. These fibers then glued and treated can then be used in the form of mats or be shredded in the form of flakes.

It is also envisaged in the context of the invention to treat the fibrous material already in the form of a fiber mat, by spraying the emulsion on the surface of the mattress in particular.

Several silicones can be combined in the emulsion used (the aqueous solvent of which evaporates during the preparation of the product).

The fibrous material according to the invention in its first variant is very effective for absorbing all types of oils or hydrocarbons, in particular those of these products which have a viscosity of between

8000 and 15000 centipoises. Generally, it is able to absorb between

15 and 50 times at least its weight of this type of oil / hydrocarbons.

As seen previously, a particularly interesting application concerns the treatment of oil spills, to selectively absorb pollutants without sinking to the bottom of the water. Other applications are also promising, in particular in the field of filtration. Finally, this type of material can also be used to “mop up” petrol or oil used in cars or trucks, especially in garages. This material can thus be available in the form of small panels (“pads” in English) which are placed in the appropriate place to recover the drain oil, for example.

The present invention also relates, in a second variant, to sorbent materials suitable for absorbing / adsorbing liquids, in particular aqueous liquids, in particular for the purpose of recovering different types of pollutants / effluents soluble in the aqueous phase or in certain organic solvents.

The same type of fibrous material as in the first variant is targeted. Sorbents are useful in medical, personal hygiene and pollutant recovery applications, among others. Fibrous materials such as wool and felts, including glass fiber materials, have been used for such applications. Figure 7 illustrates a mass of traditional insulating material made of glass fibers 10 in contact with a quantity of water 12 placed on a solid substrate 14.

U.S. Patents 5,215,407 and 5,078,890, for example, respectively describe the use of loose (i.e., unbound) and fiberglass fiberglass (i.e. related) as a means of cleaning up spills of oils and other liquid pollutants. U.S. Patent No. 5,215,407 describes the use of shredded blown glass fiber bundles for the absorption of materials such as oil, water and other surfaces. For such spills, glass fibers are preferred which preferentially absorb oil rather than water. US Patent No. 5,078,890 describes the use of felts composed of mineral fibers for the absorption of petroleum products from bodies of water. The felts include glass wool or rock wool, and include highly compressed fibers. Before compression, the fibers are cut into particles of less than 4 cm. The fibers are compressed with a binding agent which is preferably made of a water-repellent material, thus accentuating the hydrophobicity of the felts. Such hydrophobic materials may not be suitable for the absorption of water and aqueous liquids.

Therefore, there is an ongoing need for materials capable of sorbing liquids, especially water-soluble and water-based liquids. An aspect of the invention in its second variant is therefore a sorbent material comprising a glass fiber material and at least one hydrophilic particulate material.

Another aspect of the invention is a method of sorption of a liquid, comprising contacting the liquid with a sorbent material comprising a glass fiber material and at least one hydrophilic particulate material. The invention according to the second variant is the subject of claims 13 to 19.

> Figure 7 is a view illustrating the characteristic ability a traditional fiberglass material to sorb water; Figure 8 is a view, similar to Figure 7, of a sorbent glass fiber material according to the present invention, with respect to water; and ^• Figure 9 is a graphical illustration of the relative sorbency of water of several samples of traditional glass fiber materials and glass fiber sorbents according to the present invention.

It has been found that it is possible to use mineral fibers, for example glass, in combination with absorbent polymeric materials in order to form sorbent materials. Sorbents are particularly useful for absorbing water and aqueous liquids. Depending on the composition of the polymer particles, the flammability of the materials of the invention can be reduced compared to traditional absorbent materials comprising fibers. The sorbent materials of the present invention provide improved sorption compared to traditional fibrous absorbent materials and traditional absorbent materials containing absorbent particles. The term "sorbent" has the same meaning as in the first variant (the absorption of a liquid means that the liquid penetrates inside the sorbent material, while the adsorption of a liquid means that the liquid is attracted and maintained on the surface of the sorbent). The sorbent materials of the present invention may be referred to as "super-sorbents". The term "super-sorbent" denotes materials comprising sorbent particles, in addition to sorbent materials made of mineral fibers (glass), and can absorb several times their weight, such as 10 or fifteen times their weight, in liquid. The sorbent particles provide improved sorbency compared to mineral fiber materials alone.

Figure 8 illustrates a mass of sorbent fiber material glass 110 in accordance with the present invention, in contact with and adsorbing a quantity of water 12 disposed on a solid substrate 14. The glass fibers 110 may comprise a mass of loose, unrelated glass fibers, or bound glass fibers , like an insulation sheet. Bulk mineral fibers are commercially available, for example, in the form of fiberglass (or rock) insulation commonly referred to as "blown wool" insulation. The bonded fibrous material can comprise a binder such as a hardened phenolic binder or the like (this binder generally results from the drying and crosslinking of aqueous-based sizing compositions containing a resin based on phenol, formaldehyde and generally d 'urea). Examples of suitable fibrous materials for use in accordance with the present invention include Insul-Safe III ^® blow-off insulation manufactured by Certain Teed Corporation of Valley Forge, PA; ¹ "Rich-R blown insulation manufactured by Johns Manville of Denver, CO; and Thermacube ^™ insulation manufactured by Owens-Coming Corp. of Toledo, OH. The mineral wool sorbent of the invention further comprises an amount hydrophilic sorbent particles 16 dispersed throughout the mass of fibers. If desired, the sorbent materials of the invention may be placed in a sock or arrow, and the glass fiber material may be shredded, as described in United States Patent No. 5,215,407, the disclosure of which is incorporated herein by reference in its entirety. If desired, the materials may also include particles of additional materials, such as cork or polystyrene foam .

For the particles 16, any commercially available hydrophilic particulate material can be used, capable of absorbing several times its weight in water or in aqueous solution, preferably at least about 10 to about 100 times its weight. For example, the particles 16 can comprise modified starches or high molecular weight acrylic polymers containing hydrophilic groups, such as those described in U.S. Patent No. 4,429,001, the disclosure of which is incorporated herein by reference in its entirety. U.S. Patent No. 4,429,001 describes sorbent particles composed of modified food starches and high molecular weight acrylic polymers containing hydrophilic groups for absorbing water, and absorbent alkylstyrene particles for absorb liquids other than water. Other suitable particles are described in US Patent No. 3,670,731, the disclosure of which is incorporated herein by reference in its entirety. US Pat. No. 3,670,731 describes the use of particles composed of a colloidal material, in association with a support sheet, in order to sorb the fluids. The colloidal material is composed of a hydrocolloidal polymer having a particular degree of crosslinking, so that it is insoluble in water but swells when it absorbs liquid. The polymers described include crosslinked polyacrylamides, crosslinked sulfonated polystyrene and mixtures thereof. Still other suitable particles include crosslinked polyacrylates and polymethacrylates, and crosslinked acrylate / methacrylate copolymers. Other suitable polymeric materials suitable for the particles used in the present invention are polymers formed from acrylic acid or its salts, copolymerized with at least one other hydrophilic monomer, and other polymers described in US Pat. 4,914,170, the disclosure of which is incorporated herein by reference in its entirety. Crosslinked polyacrylate particles useful in the methods and compositions of the present invention include those sold by Emerging Technologies Inc. of Greensboro, NC

When particles are used in combination with glass fiber materials in the methods and compositions of the present invention, the preferred amount of particles will generally be determined by factors such as the desired absorbency, in compromise with cost . For example, the amount of particles used can be from about 5 percent by weight to about 20 percent by weight (up to 40 percent by weight optionally), preferably from about 10 percent by weight to about 15 percent by weight, based on the weight of the material fibrous. The particle size is not critical and can be, for example, from about 50 to about 3000 micrometers in average diameter, preferably from about 75 to about 1500 micrometers. Although the illustrative size ranges are provided in average diameters, the particles need not be spherical. On the contrary, the particles can be of any shape and, in the case of non-spherical particles, the illustrative mean diameters cited above denote the largest dimension of a non-spherical particle. A mixture of two or more types of particles can be used.

The particles 16 can be combined with mineral fibers 10 by any method known to those skilled in the art for the essentially uniform dispersion of the particles throughout the mass of fibers. For example, the particles 16 and the glass fibers 10 can be placed together in a vase (not shown), the vase then being vigorously agitated for a period sufficient to impregnate the glass fibers with the particles. The period and intensity of stirring will vary depending on the fiber density of the glass fibers 10 and the size of the particles 16. Alternatively, the glass fibers 10 may be impregnated with the particles 16 at the time of manufacture. a similar manner to that disclosed in US Patent No. 3,670,731. However, the particles 16 are preferably incorporated into glass fibers 10 by stirring at a speed and for a period sufficient to disperse the particles in a substantially uniform manner in the entire fibrous matrix.

The present invention in its second variant is further described in the following examples. The examples are purely illustrative of the present invention and should not be interpreted as limiting the scope of the invention in any way. EXAMPLES

Tests were carried out by comparing the sorbency of bulk and bonded traditional mineral (glass) fibers 10 and bulk and bonded sorbent glass fibers 110. Four samples were prepared, each sample comprising 30 grams of glass fibers . The unbound and bound 110 samples further included 4 grams (13.3 percent by weight, based on the weight of glass fibers) of crosslinked polyacrylate particles 16 from Emerging Technologies Inc. of Greensboro, NC Each of the four samples was been placed in a tray filled with water. Each sample was allowed to soak the water until it was completely saturated. Then the samples were placed on a V inch mesh screen and allowed to drip free. After five minutes, the samples were removed from the screens and weighed to determine the total amount of water retained by each sample. The results are illustrated in FIG. 9. As illustrated, the sample containing traditional bulk glass fibers 10 sorbed approximately 12 times its weight in water, while the sample containing bulk glass fibers 110 and particles according to the present invention has sorbed about 15 times its weight in water. The sample containing traditional bonded batting glass fibers 10 sorbed approximately 28 times its weight in water, while the sample containing bonded batt glass fibers 110 and particles according to the present invention sorbs approximately 33 times its weight in water. More generally, the unbound fibrous materials associated with particles according to the invention are capable of absorbing between 10 and 20 times their weight in water, while the bonded fibrous materials associated with the same particles are capable of absorbing between 20 and 40 times their weight in water. Thus, Figure 9 illustrates the improved ability of loose and bonded glass fiber materials 110 modified by particles 116 according to the present invention, in its second variant, to sorb water compared to the suitability of traditional bulk and bonded glass fiber materials.

The sorbent materials of the present invention, in its second variant, can be used, for example, to clean up spills of water-soluble pollutants in a body of water. When used to remove a water-soluble pollutant discharged into a body of water, the sorbent materials can simply be thrown onto the spill, the pollutant material being quickly sorbed along with its aqueous solvent. The same method can be used when the pollutants are in aqueous solution and discharged onto terrestrial structures. When the spill is on land and the pollutant is undiluted, the pollutant can be diluted with water before spreading the sorbent material on it, in order to ensure a complete sorption of the pollutant.

It is understood that these various modifications of the details, including the materials, which have been described and illustrated above in order to explain the nature of the invention in this second variant, can be carried out by a person skilled in the art. without departing from the principles and the scope of the invention. Although the invention has been described in terms of illustrative embodiments, it is not limited thereto. On the contrary, the appended claims are to be interpreted generally as encompassing other variants and embodiments of the invention which can be carried out by those skilled in the art without departing from the scope and range of equivalents. the invention.

The fibrous material with particles according to the second variant of the invention can thus "sorb" quantity of water-soluble pollutants, in particular industrial liquid effluents, paints, coolant used in vehicles, industrial waste from electrolytic deposits (" electro-plating ”) or the refinement of gold. The invention is also effective with regard to numerous non-aqueous solvents, in particular chlorinated solvents such as trichlorethylene.

Claims

1. Sorbent material comprising a fibrous material associated with an oleophilic coating and / or with a hydrophilic particulate material.

2. Sorbent material according to claim 1, characterized in that the fibrous material comprises mineral fibers of the glass fiber or rock fiber type, or cellulosic fibers.

3. Sorbent material according to claim 2, characterized in that the fibers are bound or unbound, in bulk.

4. Sorbent material according to one of claims 1 to 3, characterized in that the oleophilic coating mainly comprises, in particular essentially, one (of) silicone (s).

5. sorbent material according to one of the preceding claims, characterized in that said coating is provided in an amount of from about 0.01 to about 1.0%, in particular from 0.05 to 0.5% by weight of silicone (s) relative to the weight of the fibers.

6. Sorbent material according to one of the preceding claims, characterized in that said coating further comprises at least one dust suppression agent, in particular in the form of oil (s).

7. Sorbent material according to claim 6, characterized in that the coating comprises from 1.0% to 3.0% of oil (s).

8. Sorbent material according to one of the preceding claims, characterized in that it is provided with the oleophilic coating, in that it is capable of absorbing at least 15 to 50 times its weight in oils or hydrocarbons which have in particular a viscosity between 8000 and 15000 centipoise and in that it has a high buoyancy with respect to water.

9. A method of manufacturing a sorbent material according to one of the preceding claims, characterized in that an amount of fibrous material is selected, in particular unbound, and in that it is coated at least in part with a oleophilic coating mainly comprising, in particular essentially, a silicone (s).

10. Method according to claim 9, characterized in that the fibrous material is based on mineral glass or rock fibers and in that an said emulsion containing the silicone (s) is sprayed onto said fibers under the devices for manufacturing said fibers, in particular under the plates of centrifugation, before that they are not assembled.

11. Method according to claim 9 or claim 10, characterized in that an emulsion containing the silicone (s) is sprayed onto the fibrous material already in the form of a mattress.

12. Application of the sorbent material associated with an oleophilic coating according to one of claims 1 to 8 or obtained according to the process according to one of claims 9 to 11 to the depollution of bodies of water by oils / hydrocarbons, as a filter material, or to absorb used vehicle oil / hydrocarbons.

13. Sorbent material according to one of claims 1 to 3, characterized in that the amount of hydrophilic particulate material is from about 5 percent by weight to about 20 percent by weight, relative to the weight of the fibrous material.

14. sorbent material according to one of claims 1 to 3 or according to claim 13, characterized in that the hydrophilic particulate material is chosen from the group consisting of modified starches, of high molecular weight acrylic polymers having hydrophilic groups, a crosslinked polyacrylamide, a crosslinked sulfonated polystyrene, crosslinked polyacrylates, crosslinked polymethacrylates, crosslinked copolymers of acrylates and methacrylates, and mixtures thereof.

15. Sorbent material according to one of claims 1 to 3 or one of claims 13 or 14, characterized in that the average size of the particles of the particulate material is between 50 and 3000 micrometers, in particular between 75 and 1500 micrometers .

16. Sorbent material according to one of claims 13 to 15, characterized in that it is capable of absorbing between 10 and 20 times at least its weight in water if it uses an unbound fibrous material, and between 20 and 40 at least times its weight in water if it uses a bonded fibrous material.

17. A method of manufacturing a sorbent material according to one of claims 1 to 3 or according to one of claims 13 to 16, characterized in that an amount of fibrous material and an amount of particulate material are selected and this gives a homogeneous dispersion of the particulate material in the fibrous material by mechanical stirring.

18. A method of manufacturing a sorbent material according to one of claims 1 to 3 or according to one of claims 13 to 16, characterized in that the particulate material is introduced in the form of a colloidal suspension in the fibrous material.

19. Application of the sorbent material associated with a hydrophilic particulate material according to one of claims 1 to 3 or 13 to 16 or obtained according to the process according to claim 17 or claim 18 to the absorption of organic solvents of the trichlorethylene type or absorption of water-soluble pollutants such as paint, coolant, industrial effluents.