Granulated product of at least one of expanded milled perlite, diatomaceous earth, and sepiolite as an absorbent

Abstract

A granulated product comprising a binder and at least one of expanded milled perlite particles, diatomaceous earth particles, and sepiolite particles, wherein the particles are bound together by the binder to form pores between the particles, and the granulated product has a D of about 150 to about 2000 μm 50 The granulated product.

Description

Technical Field

[0001] The present disclosure relates to a granulated product containing a binder and at least one of expanded milled perlite particles, diatomaceous earth particles, and sepiolite particles, a method for preparing a granulation material, an absorbent material containing the granulation material, an animal feed composition containing the granulation material, and a method for treating fluid spillage using the granulation material.

Background Art

[0002] Perlite is a naturally occurring amorphous volcanic glass having a relatively high water content. When rapidly heated, the water is converted to steam, expanding the glass to form a foamed structure. The lightweight expanded perlite foamed structure is milled and classified to be suitable for a wide variety of applications. Expanded milled perlite is generally used as a lightweight absorbent material in applications that require absorption of a target liquid. Expanded milled perlite is already used as a carrier for animal feed that absorbs liquid nutrients. Further, expanded perlite is an ideal medium for cleaning fluid spillage. Diatomaceous earth products are generally obtained from diatomaceous earth (also called "DE" or "diatomite"), a sediment rich in biogenic silica (silica produced or brought about by organisms) in the form of the silica-like skeletons (frustules) of diatoms. Diatoms are generally microscopic unicellular golden algae of the class Bacillariophyceae that possess a decorative silica-like skeleton of various and complex structures, including two valves that fit together in a state closely resembling pillboxes in living diatoms. Diatomaceous earth may be formed from the fossils of diatoms carried by water, and thus deposits of diatomaceous earth can be found near any current or former body of water. Those deposits are generally divided into two categories based on freshwater and saltwater sources.

[0003] Sepiolite is an opaque, fibrous magnesium hydrosilicate that is white, grey, or cream-colored. This light, porous clay is said to resemble sea foam. Sepiolite, like milled perlite, is known to have good adsorption properties and is an abundantly available material. It is considered desirable to produce a granulated product comprising a binder and at least one of expanded milled perlite particles, diatomaceous earth particles, and sepiolite particles, having improved absorption capacity, constant fluidity when the incorporation of liquid is increased, and reduced dust levels when compared to expanded perlite typically used.

Summary of the Invention

[0004] According to a first aspect, there is provided a granulate comprising a binder and at least one of expanded milled perlite particles, diatomaceous earth particles, and sepiolite particles, i) the expanded milled perlite particles having a D 50 of about 5 to about 40 μm, ii) the diatomaceous earth particles having a D 50 of about 5 to about 40 μm, iii) the sepiolite particles having a D 50 of about 5 to about 100 μm, iv) the granulate having a D 50 of about 150 to about 2000 μm, the particles being bound together by the binder to form pores between the particles, wherein the granulate is provided. According to a second aspect, there is provided an absorbent material comprising the granulate according to the first aspect. According to a third aspect, there is provided a method for treating a fluid spill, comprising applying the absorbent material according to the second aspect to the fluid spill such that the fluid is absorbed by the absorbent material. According to a fourth aspect, there is provided an animal feed comprising the granulate according to the first aspect. According to a fifth aspect, there is provided a method for preparing the granulate according to the first aspect, comprising spray-drying the milled expanded perlite particles together with a binder and performing a curing step. Those skilled in the art will understand that, unless mutually exclusive, the features described with respect to any one of the above aspects can be applied to any other aspect by making appropriate changes. Further, unless mutually exclusive, any feature described in this specification may be applied to any aspect and / or may be combined with any other feature described in this specification. Next, embodiments will be described by way of example only with reference to the drawings.

Brief Description of the Drawings

[0005]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0006] It has surprisingly been found that granulates of at least one of expanded milled perlite, diatomaceous earth, and sepiolite using a binder result in a product having a high absorption rate, a certain fluidity, and a minimized dust level.

[0007] Expanded milled perlite particles Perlite typically contains the following components: silicon dioxide, aluminum oxide, sodium oxide, potassium oxide, iron oxide, magnesium oxide, calcium oxide, water, and small amounts of other metal elements. The perlite particles of the present invention are in the form of expanded perlite. Typically, expanded perlite contains one or more cells or portions of cells, which are void spaces partially or entirely surrounded by glass walls, usually formed from the expansion of gas when the glass is in a softened state. The process for expanding perlite may include heating the perlite in an expansion furnace in air to a temperature of at least about 700 °C, typically between 800 °C and 1100 °C. An exemplary process for producing expanded perlite is described in US Patent Application Publication No. 2006 / 0075930, the entire contents of which are incorporated herein by reference. Expanded perlite typically has a bulk volume up to 20 times the volume of the unexpanded material. According to the present invention, the perlite is milled after being expanded in an expansion furnace.

[0008] Unless otherwise specified, the particle size characteristics referred to herein with respect to the expanded milled perlite particles are as measured by the method used in the technical field of laser light scattering using a CILAS 1064L particle size analyzer supplied by CILAS (or by other methods that essentially give the same results). In the laser light scattering technique, the size of particles in a powder, suspension, or emulsion can be measured using the diffraction of a laser beam based on the application of Fraunhofer and Mie theories. Such machines provide a measurement and plot of the cumulative volume percentage of particles having a size less than a given e.s.d value, which in the art is referred to as the "equivalent spherical diameter" (e.s.d). The average particle size d 50 is the value of the particle e.s.d determined in this way, such that 50 volume % of the particles have an equivalent spherical diameter less than that d 50 value. According to the present invention, the expanded milled perlite particles have a d 50 of from about 5 to about 40 μm, for example from about 10 to about 35 μm, or from about 15 to about 30 μm, or from about 20 to about 25 μm.

[0009] In certain embodiments, the expanded milled perlite particles have a density of about 0.05 g / cm3 ~ about 0.20 g / cm 3 , for example, about 0.06 g / cm 3 ~ about 0.19 g / cm 3 , for example, about 0.07 g / cm 3 ~ about 0.18 g / cm 3 , for example, about 0.08 g / cm 3 ~ about 0.17 g / cm 3 , for example, about 0.09 g / cm 3 ~ about 0.16 g / cm 3 , for example, about 0.10 g / cm 3 ~ about 0.15 g / cm 3 , for example, about 0.11 g / cm 3 ~ about 0.14 g / cm 3 , for example, about 0.12 g / cm 3 ~ about 0.13 g / cm 3 and have a bulk density of

[0010] Diatomaceous earth particles Unless otherwise specified, the particle size characteristics referred to herein with respect to diatomaceous earth particles are measured by a method used in the field of laser light scattering using a CILAS 1064L particle size analyzer supplied by CILAS (or by other methods that essentially give the same results). In the laser light scattering technique, the size of particles in powders, suspensions, and emulsions can be measured using the diffraction of a laser beam based on the application of Fraunhofer and Mie theories. Such machines result in the measurement and plotting of the cumulative volume percentage of particles having a size called the "equivalent spherical diameter" (e.s.d) that is less than a given e.s.d value. The average particle size d 50 is this determined value of the particle e.s.d at which 50 volume% of the particles have an equivalent spherical diameter less than that d 50 value. According to the present invention, the diatomaceous earth particles have a d 50 of about 5 to about 40 μm, for example, about 10 to about 35 μm, or about 15 to about 30 μm, or about 20 to about 25 μm. In certain embodiments, the diatomaceous earth particles have a density of about 0.05 g / cm 3 ~ about 0.20 g / cm 3, for example, about 0.06 g / cm 3 ~ about 0.19 g / cm 3 , for example, about 0.07 g / cm 3 ~ about 0.18 g / cm 3 , for example, about 0.08 g / cm 3 ~ about 0.17 g / cm 3 , for example, about 0.09 g / cm 3 ~ about 0.16 g / cm 3 , for example, about 0.10 g / cm 3 ~ about 0.15 g / cm 3 , for example, about 0.11 g / cm 3 ~ about 0.14 g / cm 3 , for example, about 0.12 g / cm 3 ~ about 0.13 g / cm 3 and have a bulk density of

[0011] Sepiolite particles Sepiolite is a naturally occurring clay mineral. It is a lightweight non-swelling and porous hydrated magnesium silicate. The particle size characteristics referred to herein with respect to sepiolite particles are as measured by a method used in the technical field of laser light scattering using a CILAS 1064L particle size analyzer as supplied by CILAS (or by other methods that give essentially the same results). In the laser light scattering technique, the size of particles in powders, suspensions, and emulsions can be measured using the diffraction of a laser beam based on the application of the Fraunhofer and Mie theories. Such machines provide the measurement and plotting of the cumulative volume percentage of particles having a size called the "equivalent spherical diameter" (e.s.d) that is less than a given e.s.d. The average particle size d 50 is the value thus determined of the particle e.s.d at which 50 volume% of the particles have an equivalent spherical diameter less than that d 50 value.

[0012] According to the present invention, the sepiolite particles have a d of about 5 to about 100 μm, for example about 10 to about 90 μm, or about 20 to about 80 μm, or about 30 to about 70 μm, or about 40 to about 60 μm, about 10 to about 50 μm, or about 20 to 40 μm50 has. In certain embodiments, the sepiolite particles have a bulk density of from about 0.05 g / cm 3 to about 0.30 g / cm 3 , such as from about 0.06 g / cm 3 to about 0.19 g / cm 3 , such as from about 0.07 g / cm 3 to about 0.18 g / cm 3 , such as from about 0.08 g / cm 3 to about 0.17 g / cm 3 , such as from about 0.09 g / cm 3 to about 0.16 g / cm 3 , such as from about 0.10 g / cm 3 to about 0.15 g / cm 3 , such as from about 0.11 g / cm 3 to about 0.14 g / cm 3 , such as from about 0.12 g / cm 3 to about 0.13 g / cm 3 .

[0013] Granules According to the present invention, at least one of expanded milled perlite particles, diatomaceous earth particles, and sepiolite particles is bound together using a binder to form granules. Granulation is an operation or process in which primary powder particles adhere to form a larger entity of multiple particles called fines or granules. In certain embodiments, the granulate comprises, consists of, or consists essentially of expanded milled perlite particles and a binder. In certain embodiments, the granulate comprises, consists of, or consists essentially of diatomaceous earth particles and a binder. In certain embodiments, the granulate comprises, consists of, or consists essentially of sepiolite particles and a binder. In certain embodiments, the granulate comprises, consists of, or consists essentially of a blend of expanded milled perlite particles and diatomaceous earth particles with a binder. In certain embodiments, the granulate comprises, consists of, or consists essentially of a blend of expanded milled perlite particles and sepiolite particles with a binder. In certain embodiments, the granulate comprises, consists of, or consists essentially of a blend of diatomaceous earth particles and sepiolite particles with a binder. In certain embodiments, the granulate comprises, consists of, or consists essentially of a blend of expanded milled perlite particles, diatomaceous earth particles, and sepiolite particles with a binder.

[0014] At least one of the expanded milled perlite particles, diatomaceous earth particles, and sepiolite particles is bound together by a binder to form what is known as pores or, if not, interstitial void spaces between the particles. In some embodiments, the pores have a measurable pore size as described in the following experimental section. In certain embodiments, the median pore size is from about 1 g / cm 3 to about 6 g / cm 3 , or about 1.1 g / cm 3 , or about 1.2 g / cm 3 , or about 1.3 g / cm 3 , or about 1.4 g / cm 3 , or about 1.5 g / cm 3 , or about 1.6 g / cm 3 , or about 1.7 g / cm 3 , or about 1.8 g / cm 3 , or about 1.9 g / m 3 , or about 2.0 g / m 3 .

[0015] According to the present invention, the granulated product has a d of about 150 to about 2000 μm, for example about 200 μm to about 1900 μm, or about 300 μm to about 1800 μm, or about 400 μm to about 1700 μm, or about 500 μm to about 1600 μm, or about 600 μm to about 1500 μm, or about 700 μm to about 1400 μm, or about 800 μm to about 1300 μm, or about 900 μm to about 1200 μm, or about 1000 μm to about 1100 μm, or about 200 μm to about 600 μm, for example about 350 μm to about 550 μm, or about 400 μm to about 500 μm, or about 600 μm to about 1900 μm, for example about 700 μm to about 1800 μm, or about 800 μm to about 1600 μm, or about 900 μm to about 1500 μm, or about 1000 μm to about 1400 μm, or about 1100 μm to about 1300 μm, as determined by the laser diffraction method (as described above). 50 The granulated product may have a d of about 200 μm to about 1000 μm, or about 300 μm to about 900 μm, or about 400 μm to about 800 μm, or about 500 μm to about 700 μm as determined by laser. 50 It may have a d of about 200 μm to about 1000 μm, or about 300 μm to about 900 μm, or about 400 μm to about 800 μm, or about 500 μm to about 700 μm as determined by laser.

[0016] In certain embodiments, the granulated product has a bulk density of about 0.1 g / cm 3 to about 0.50 g / cm 3 e.g., about 0.15 g / cm 3 to about 0.45 g / cm 3 e.g., about 0.20 g / cm 3 to about 0.40 g / cm 3 e.g., about 0.20 g / cm 3 to about 0.35 g / cm 3 e.g., about 0.25 g / cm 3 to about 0.30 g / cm 3 ​The granulated product of the present invention may have a measurable BET surface area. The BET specific surface area refers to the surface area of the particles of the granulated material per unit mass, which is determined according to the BET method by the amount of nitrogen adsorbed on the surface of the particles to form a monomolecular layer that completely covers the surface area (measurement according to the BET method, AFNOR standards X11-621 and 622, or ISO 9277). The details of the BET specific surface area measurement method used in the preparation of this application are described in the examples.

[0017] The granulated product may have a BET specific surface area of about 1.5 m 2 / g or more, for example about 1.6 m 2 / g or more, or about 1.7 m 2 / g or more, or about 1.8 m 2 / g or more, or about 1.9 m 2 / g or more, or about 2.0 m 2 / g or more, or about 2.5 m 2 / g or more, or about 3.0 m 2 / g or more, or about 5.0 m 2 / g or more, or about 10 m 2 / g or more (for example, 10.0 m 2 / g), or about 20 m 2 / g or more (for example, 11.0 m 2 / g). The granulated product may have a BET specific surface area of about 50 m 2 / g or less (for example, 50.0 m 2 / g), for example about 40 m 2 / g or less (for example, 40.0 m 2 / g), or about 30 m 2 / g or less (for example, 30.0 m 2 / g), or about 20 m 2 / g or less (for example, 20.0 m 2 / g), or about 15 m 2 / g or less (for example, 15.0 m 2 / g), or about 12 m 2 / g or less (for example, 12.0 m 2 / g), or about 11 m 2 / g or less (for example, 11.0 m 2 / g), or about 10 m 2 / g or less (for example, 10.0 m 2 / g), or about 8.0 m2 / g or less, or about 7.0m 2 / g or less, or about 6.0m 2 The granules may have a BET specific surface area of about 1.5 m 2 / g~about 50m 2 / g (e.g., 50.0 m 2 / g), for example, about 2m 2 / g~about 40m 2 / g (e.g., 40.0 m 2 / g), or about 5m 2 / g ~ approx. 30m 2 / g (e.g., 30.0 m 2 / g), or about 10m 2 / g~about 20m 2 / g (e.g., 20.0 m 2 The specific surface area may be a BET specific surface area (.times.1 / g).

[0018] In certain embodiments, the granulation has an angle of repose of up to about 38° as measured by the angle of repose using an EFT-01 powder flow tester (Funnel Method), the granulation has an absorption capacity of at least 150% as measured using the Westinghouse method described herein in the Experimental Section and utilizing dioctyl adipate as the absorbent, and has a dust content of less than 10 as measured by a Dustmon RD 100 dust analyzer. The angle of repose of a granulated material is the steepest angle of descent or inclination with respect to a horizontal surface at which the material can be stacked without collapsing. The morphology of the material affects the angle of repose. When bulk granular material is poured onto a horizontal surface, a cone-shaped pile will be formed. The internal angle between the surface of the pile and the horizontal surface is known as the angle of repose and is related to the density, surface area, and shape of the particles, as well as the coefficient of friction of the material. Materials with low angles of repose will form flatter piles than materials with high angles of repose. Thus, smooth, rounded sand grains cannot stack as steeply as coarse, interlocking sand. The method for calculating the angle of repose is described in more detail in the experimental section below.

[0019] In certain embodiments, the angle of repose (of the dry product) is at most about 38°, such as at most 37°, such as at most 36°, such as at most 35°, such as at most 34°, such as at most 33°, such as at most 32°, such as at most 31°, such as at most 30°. In certain embodiments, the granulate has an advantageously low dust content of less than 10, such as less than 9 or 8 (measured using a Dustmon RD 100 dust analyzer (available from Retsch®)). The method for calculating the value of the dust content is described in more detail in the experimental section.

[0020] Expanded milled perlite, diatomaceous earth, and sepiolite are already known for their water retention ability and strong water absorption capacity. This absorption capacity is further increased by granulating at least one of expanded milled perlite particles, diatomaceous earth particles, and sepiolite particles with a binder. In certain embodiments, the granulate of the present invention has an absorption capacity of at least 150% (calculated as 100×(mass of the absorbed substance / mass of the composition)) calculated using the Westinghouse method described herein in the experimental section. In certain embodiments, the granulate has an absorption capacity of at least 200%, such as at least 250%, such as at least 300%, such as at least 350%, such as at least 400%, such as at least 450%, such as at least 500%.

[0021] Binder According to the present invention, at least one of expanded milled perlite particles, diatomaceous earth particles, and sepiolite particles is bound together using a binder to form a granulate. In certain embodiments, the binder is a polymer, bentonite, or lignosulfonate. In certain embodiments, the binder is a polymer. In certain embodiments, the binder consists of a single type of polymer, or in certain embodiments, the binder comprises one or more polymers. In certain embodiments, the polymer is selected from one or more of a water-soluble synthetic polymer, a natural water-soluble polymer, and a polyol. In certain embodiments, the polymer is a combination of these types of polymers.

[0022] In certain embodiments, the binder comprises or consists of a water-soluble synthetic polymer selected from, for example, polyvinyl alcohol (PVA), polyethylene glycol, urea formaldehyde, polyacrylamide, microcrystalline cellulose, polyacrylate, acrylic / maleic acid copolymer, and polyvinyl pyrrolidone. In certain embodiments, the binder comprises or consists of a natural water-soluble polymer, such as xanthan gum, sodium alginate, potassium alginate, lignosulfonate, locust bean gum, pectin, dextran, carrageenan, agar, xanthan gum, guar gum, gum arabic (acacia), cellulose ethers such as methylcellulose and ethylcellulose, starch or starch derivatives. In certain embodiments, the binder comprises or consists of a polyol. The term "polyol" means an organic compound containing a number of hydroxyl groups. The polyol may be a low molecular weight polyol such as glycerol or pentaerythritol. Alternatively, the polyol may be a sugar alcohol, which is a class of low molecular weight polyols obtained by the hydrogenation of sugars, such as erythritol, hydrogenated starch hydrolysate, isomalt, lactitol, maltitol, mannitol, sorbitol, and xylitol. Also intended to be included in this definition are derivatives of polyols, such as sorbitan monolaurate, which is a mixture of esters formed from polyols derived from fatty acid lauric acid and sorbitol.

[0023] In certain embodiments, the binder is selected from polyvinyl alcohol, sodium alginate, potassium alginate, lignosulfonate, urea-formaldehyde, agar, carrageenan, guar gum, cassia gum, xanthan gum, cellulose, gum arabic (acacia), microcrystalline cellulose, methyl cellulose, ethyl cellulose, sorbitan monolaurate, starch or starch derivatives, bentonite, and combinations thereof. In certain embodiments, the binder comprises or consists of polyvinyl alcohol having a molecular weight greater than about 90,000 g / mol, or greater than about 100,000 g / mol, or greater than about 120,000 g / mol, or greater than about 150,000 g / mol. In certain embodiments, the binder is a crosslinked binder that is a reaction product of a polymer and a crosslinking agent. Crosslinking is the formation of chemical bonds between polymer chains to form a three-dimensional network structure of connected molecules. The polymer may be selected from the list of polymers described above. The crosslinking agent is well known in the art and may be selected depending on the type of polymer.

[0024] In certain embodiments, the crosslinking agent is the following (i) Dicarboxylic acids including oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, tartaric acid, tartronic acid, aspartic acid, glutamic acid, fumaric acid, itaconic acid, maleic acid, traumatic acid, camphoric acid, phthalic acid and its derivatives containing at least one boron or chlorine atom, tetrahydrophthalic acid and its derivatives containing at least one chlorine atom, isophthalic acid, terephthalic acid, mesaconic acid, and citraconic acid, (ii) Tricarboxylic acids including citric acid, tricarballylic acid, 1,2,4-butanetricarboxylic acid, aconitic acid, hemimellitic acid, trimellitic acid, and trimesic acid, (iii) Tetracarboxylic acids including 1,2,3,4-butanetetracarboxylic acid and pyromellitic acid, (iv) Polycarboxylic acids such as EDTA, (v) Unsaturated carboxylic acids including (meth)acrylic acid, crotonic acid, isocrotonic acid, maleic acid, cinnamic acid, 2-methylmaleic acid, fumaric acid, itaconic acid, 2-methylitaconic acid, α,β-methylene glutaric acid, and monoesters of unsaturated dicarboxylic acids, and vinyl monomers which are styrenes optionally substituted with an alkyl, hydroxyl or sulfonyl group, or a halogen atom, (meth)acrylonitrile, (meth)acrylamides optionally substituted with a C1-C10 alkyl group, alkyl (meth)acrylates, glycidyl (meth)acrylates, butadiene, and vinyl esters (vi) Inorganic acids such as boric acid and phosphoric acid is an acid selected from one or more of the above.

[0025] In certain embodiments, the crosslinking agent is selected from the following list: primary amines (e.g., N-hydroxysuccinimide esters), carbonyls (such as acrylic resins), inorganic acids (such as phosphoric acid), Lewis acids (e.g., boric acid or aluminum chloride), and carboxylic acids. In certain embodiments, the crosslinking agent is a carboxylic acid selected from dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, polycarboxylic acids, and unsaturated carboxylic acids. In certain embodiments, the carboxylic acid is a polycarboxylic acid such as citric acid or succinic acid. In certain embodiments, the carboxylic acid is an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, and maleic acid. In certain embodiments, the binder is a reaction product of polyvinyl alcohol and citric acid. Carboxylic acids are a preferred type of crosslinking agent due to their low toxicity and cost. Polyvinyl alcohol is also known to be non-toxic and biodegradable.

[0026] In certain embodiments, the binder is present in an amount of from about 0.1% to about 40% by weight, or from about 1% to about 35% by weight, or from about 5% to about 30% by weight, or from about 10% to about 25% by weight, or from about 15% to about 20% by weight, or from about 1% to about 5% by weight of the total weight of the granulate. In certain embodiments, the binder consists of a polymer such that 100% by weight of the binder is polymer. In certain embodiments, in addition to the polymer component, the binder contains a cross-linking agent, and the mass ratio of the polymer component to the cross-linking agent is 1:1 to 3:1; or 1:1 to 3.5:1, or 1:1 to 1:4. According to an embodiment, the polymer component is polyvinyl alcohol and the cross-linking agent is a carboxylic acid; the mass ratio of polyvinyl alcohol to the carboxylic acid is 1:1 to 3:1; or 1:1 to 3.5:1, or 1:1 to 1:4.

[0027] Method for preparing granulate In certain embodiments, particles comprising at least one of expanded milled perlite particles, diatomaceous earth particles, and sepiolite particles are mixed together. The binder is first dispersed in water and sprayed onto the particles comprising at least one of expanded milled perlite particles, diatomaceous earth particles, and sepiolite particles such that the particles agglomerate and form a granulate. Following the spraying step, a curing step is carried out at a temperature of 80°C to 120°C. The curing step is typically carried out for a length of time such that the granulate dries and the binder cures. After the curing step is carried out, the water content of the granulate is below about 5% by weight of the granulate, for example less than about 3% by weight or less than about 2% by weight. The curing step is carried out for a length of time such that the water content reaches the desired level described above and may take up to 12 hours or up to 8 hours or up to 4 hours.

[0028] Absorbent material According to the present invention, there is provided an absorbent material comprising granules as already described herein. In certain embodiments, the binder is a crosslinked binder which is a reaction product of a polymer and a crosslinking agent. This type of binder is particularly strong for applications where the granules function as an absorbent material and additional hydrophobicity is required (e.g., when used for oil absorption). The inventors have found that the absorbent material is particularly useful in methods for treating fluid spills due to the improved absorption ability of the granules. "Fluid spill" means an undesirable release of fluid into the environment, such as an oil spill (e.g., from an oil tanker or a leak at a gas station), an aqueous spill (e.g., soft drinks, acid solutions, and basic solutions), a chemical spill (e.g., organic and inorganic solvents), a food spill (e.g., soup or sauce), and a body fluid spill (e.g., blood, urine, and vomit).

[0029] In some embodiments, the absorbent material may be used in a closed container for disposing of liquid toxic waste substances. In certain embodiments, the absorbent material absorbs up to 100% of the mass of the granules, such as up to 95% of the mass of the granules, or up to 90%, or up to 85%, or up to 80%, or up to 75%, or up to 70% of a fluid spill.

[0030] Animal feed composition According to the present invention, there is provided an animal feed composition comprising the granulated product described herein. In certain embodiments, the animal feed composition comprises at least one nutrient. The term "nutrient" means the basic substances including carbohydrates, proteins, fats, minerals, vitamins, and water that animals need to maintain, grow, reproduce, and have good health. The main sources of carbohydrates in animal feed are grains such as oats, wheat, barley, corn, sorghum, forage, and hay. Proteins can be derived from plants or animals such as amino acids, oil meal, fish meal, and meat scraps. Common sources of fat include fish oil, seed-derived oils such as linseed oil, sunflower, canola oil, and plant-derived oils such as corn and soybeans. Minerals may include elements such as sodium, calcium, phosphorus, sulfur, potassium, magnesium, manganese, iron, copper, cobalt, iodine, zinc, molybdenum, and selenium, which are important for the growth of healthy and fertile animals. Vitamins can be either water-soluble or fat-soluble and are broadly classified as vitamins A, B, C, D, E, and K.

[0031] The above list is not limiting, and those skilled in the art will be aware of the available nutrients and will be able to select and blend nutrient components to provide animals with a diet of the necessary nutrients, which will depend on the species of the animal. In certain embodiments, the granulation binder for the animal feed composition is selected from polyvinyl alcohol, bentonite, sodium alginate, potassium alginate, lignosulfonate, urea-formaldehyde condensation polymer, agar, carrageenan, guar gum, cassia gum, xanthan gum, cellulose, gum arabic (acacia), microcrystalline cellulose, methyl cellulose, ethyl cellulose, sorbitan monolaurate, starch or starch derivatives, and combinations thereof, and preferably the binder is polyvinyl alcohol.

[0032] In certain embodiments, the animal feed consists solely of the granules and contains no additional nutrients or ingredients. Thus, the animal feed composition may be provided such that the granules absorb and carry the liquid of interest for the desired animal feed, where the liquid of interest may be water or any liquid nutrient animal feed. One of ordinary skill in the art may recognize suitable liquid nutrient animal feeds and select the liquid of interest depending on the animal being fed. In certain embodiments, the granules absorb up to 100% of the mass of the granules, such as up to 95% of the mass of the granules, or up to 90% of the mass of the granules, or up to 85% of the mass of the granules, or up to 80% of the mass of the granules, or up to 75% of the mass of the granules, or up to 70% of the mass of the granules, of the liquid of interest.

[0033] In certain embodiments, the binder is present in an amount of from about 0.1% to about 40% by weight of the total weight of the animal feed composition, or from about 1% to about 35% by weight of the total weight of the animal feed composition, or from about 5% to about 30% by weight of the total weight of the animal feed composition, or from about 10% to about 25% by weight of the total weight of the animal feed composition, or from about 15% to about 20% by weight of the total weight of the animal feed composition, or from about 1% to about 5% by weight of the total weight of the animal feed composition.

Examples

[0034] (Example 1) The following particles were used in the tests under this example (in the granulated or non - granulated form as described below): Expanded milling perlite (EMP available from Imerys) Diatomaceous earth Binders used: polyvinyl alcohol; bentonite, and lignosulfonate 500 g of particles (either expanded milling perlite or diatomaceous earth) were placed in a mixer (Eireich mixer). 25 g of binder was dissolved in 700 g of water. The final weight percentage of the binder was 5% by weight of the total granulate. The binder composition was then sprayed onto the particles using a simple commercial sprayer.

[0035]

Table 1

[0036] PSD laser The particle size distribution (PSD) was determined using a Mastersizer 2000 manufactured by Malvern Instruments. As described above and as described in the examples, D 50 is the value of the average particle size (d50) measured by laser diffraction (standard NFX-11-666 or ISO 13320-1), and "d 50 sedi " is the value of the median diameter obtained by sedimentation using a sedigraph (standard Afnor-X-11-683 or ISO 13317-3). Reference may be made to the literature by G. Baudet and J. P. Rona, Ind. Min. Mines et Carr. Les techn. June, July 1990, pp 55-61, which shows that the lamellarity index correlates with the average ratio of the maximum dimension to the minimum dimension of the particles.

[0037] Absorbing capacity The absorbing capacity was calculated using the Westinghouse method (based on NV V19-002). To carry out this method, the sample to be tested was introduced into a liquid via a sieving device. In this case, the liquid used was dioctyl adipate. The sample was then left immersed for 20 minutes, after which the sample was removed and the excess liquid was removed. The mass of the product before and after immersion was compared to calculate the absorption of the product.

[0038] Dust analysis The Dustmon RD 100 dust analyzer (available from Retsch®) characterizes the dispersibility of powders and granulates. The DustMon RD 100 consists of a dosing control system (a sample beaker equipped with a valve and a tube, a sample collector, a light source, and a detector). The sample is poured into the sample beaker. At the start of the measurement, the valve is opened, and the sample is passed through the tube and dropped into the sample collector. The dust generated in the sample collector will be measured by the detector, and the resulting dust index will be displayed. The results provide the measured value of the maximum dust concentration in % (0 - 100% of the total dust concentration).

[0039] Density The bulk density of the sample was evaluated by measuring the sample in a test tube and comparing the volume of the sample to its mass. Specific surface area (SSA - B.E.Tm 2 / g) The BET specific surface area was determined using a method based on the standard NF X 11 - 621 named "Determination de''aire massique (surface specifique) des poudres par adsorption de gaz - Methode B.E.T. - Mesure volumetrique par adsorption d'azote a basse temperature" (Determination of the mass area (specific surface) of powders by gas adsorption - BET method - Volume measurement by nitrogen adsorption at low temperature). The method utilized a Micromeritics measuring device (available from Micromeritics Instrument Corp., USA) including a vacuum pump, a VacPrep 061 degassing section, a Tristar 3000S measuring section, and a sample holder, a Mettler AG204 scale with an accuracy of 0.1 mg, a Dewar flask, a nitrogen adsorption gas, and a helium carrier gas.

[0040] The sample was weighed near the empty sample holder (to an accuracy of 0.1 mg), and its mass M0 was recorded in grams. Subsequently, the already homogenized powder sample was introduced into the sample holder using a funnel. Sufficient space (dead volume) was left between the sample and the top of the sample holder to allow free circulation of gas. The sample holder was placed in one of the degassing stations and degassed at 250 °C under a primary vacuum of 10 Pa for approximately 20 minutes. After degassing, a sufficient volume of nitrogen was added to the sample holder to avoid introduction of air during the transfer of the sample holder from the degassing station to the measurement station. The sample holder was then attached to the measurement station, and a Dewar flask containing liquid nitrogen was placed around the sample holder. The BET measurement was started using the device control software. The device then automatically performed the following operations: - Vacuum removal of the nitrogen introduced for the movement of the sample holder; - Leak test; - Addition of helium carrier gas; - Measurement of the dead volume at ambient temperature; - Measurement of the cryogenic dead volume using liquid nitrogen; - Helium vacuum removal; - Leak test; - Addition of nitrogen and measurement of the saturation pressure at 950 mmHg; and - Acquisition of the analytical values.

[0041] The device's data acquisition and processing software plotted the transformed BET line from five measured adsorption points. The Dewar flask and then the sample holder were removed. The device was returned to ambient temperature, and the sample was weighed again near the sample holder (to an accuracy of 0.1 mg), and the mass was recorded as M2 in grams. The mass of the test portion of the sample, M, was: M = M2 - M0 was calculated according to (the unit is g). The value M was then introduced into a software calculation program that automatically calculates the BET specific surface area of the sample in units of m 2 / g.

[0042] Porosity Porosity is the percentage of interstitial void space in a granular material. The following equation: Φ = V V / V T (where Φ is the porosity, V V is the void volume, and V T is the total volume.) is used to calculate it. Porosity was measured using mercury porosimetry, which characterizes porosity by forcing mercury into the pores. Standard tests for mercury porosimetry begin with ASTM D4404 - 18.

[0043] Angle of repose The angle of repose was measured using a Manual Powder Flow Tester (EFT - 01) using ISO 8398:1989. The angle of repose is calculated as follows: Θ = tan -1 h / r (where Θ is the angle of repose, h is the height in cm of the conical pile, and r is the radius in cm.). Supplementary measurements for the angle of repose are the dynamic angle of repose (or flow angle) measured using Granudrum. The GranuDrum instrument (available from GRANUTOOLS™) is an automated powder flowability measurement technique predicted by the principle of a rotating drum. The drum is a horizontal cylinder with transparent side walls, half of which is filled with a powder sample. The drum rotates about its axis at various angular velocities from 2 to 70 rpm. In this case, the angular velocity is measured at 10 rpm and a CCD camera acquires several snapshots. At the measured rotational speed, the dynamic cohesion index is measured from the fluctuations of the interface, and the flow angle, also called the "dynamic angle of repose" in the literature, is calculated from the average interface position. A low value of the flow angle corresponds to excellent flowability.

[0044] Flowability Figure 1 shows the influence of absorption on the fluidity of powders. The powder flow, also known as fluidity, is defined as the relative movement of a mass of particles among adjacent particles and along the surface of the container wall. In other words, powder fluidity refers to the ability of the powder to flow through a specific part of the device in a desired manner. Figure 1 measures the liquid DOA% against the angle of repose to evaluate the influence of fluidity. The following samples from Table 1 were tested: Granulated EMP + 5% by mass PVA, granule particle size 200 - 600 μm Granulated EMP + 5% by mass PVA, granule particle size 600 - 1700 μm Granulated EMP + 5% by mass bentonite, granule particle size 200 - 600 μm Granulated DE, granule particle size 200 - 600 μm Granulated EMP + 5% by mass lignosulfonate, granule particle size 600 - 2500 μm Expanded perlite (without milling)

[0045] The data in Table 1 and Figure 1 show that when granules are formed using PVA as a binder according to the present invention, the powder samples achieved excellent absorption capacity (between 90 - 100%) and excellent fluidity results. Other samples (3 - 5) of the present invention showed lower absorption in some cases but still demonstrated improved fluidity compared to their non - granulated counterparts. Sample 6 showed no fluidity at all. Lignosulfonate is shown to be able to bind EMP as well, with a somewhat lower absorption but of course a good angle of repose.

[0046] SEM images were taken for the following samples from Table 1 and presented in Figure 2: a) Expanded milled perlite b) Granulated EMP + PVA (200 - 600 μm) c) Granulated EMP + lignosulfonate (200 - 600 μm) d) Granulated EMP + bentonite (200 - 600 μm) The apparatus used was a SEM FEI Quanta 200 microscope. All SEM images show proper granulation of primary EMP particles using various binders.

[0047] (Example 2)

Table 2

[0048] The Westinghouse absorption test was performed on various granules prepared using expanded granulated perlite (200 - 600 μm) and with the components described in Table 2 above. The Westinghouse method is as described above.

Claims

1. A granulated product comprising a binder and at least one of expanded milled perlite particles, diatomaceous earth particles, and sepiolite particles, wherein: i) the expanded milled perlite particles have a D50 of about 5 to about 40 μm, ii) the diatomaceous earth particles have a D50 of about 5 to about 40 μm, iii) the sepiolite particles have a D50 of about 5 to about 100 μm, iv) the granulated product has a D50 of about 150 to about 2000 μm, and the particles are bound together by the binder to form pores between the particles.

2. An angle of repose, measured by the angle of repose using an EFT-01 powder flow tester (funnel method), of at most about 38°, an absorption capacity of at least 150%, measured using the Westinghouse method described herein and utilizing dioctyl adipate as the substance to be absorbed, and a dust content of less than 10, measured by a Dustmon RD 100 dust analyzer for the granulated product according to Claim 1.

3. The granulate according to claim 1 or 2, wherein either or both of the expanded milled perlite particles and the diatomaceous earth particles have a D of about 10 to about 30 μm 50 ​

4. The sepiolite particles have a D of about 10 to about 50 μm 50 The granulated product according to any one of claims 1 to 3, having

5. The granulated product has a D of about 200 to about 600 μm or about 600 to about 1700 μm 50 The granulated product according to any one of claims 1 to 4, having the same.

6. wherein the binder is i) a polymer, or ii) a crosslinked binder that is a reaction product of a polymer and a crosslinking agent, or iii) bentonite, or iv) lignosulfonate for the granulated product according to any one of Claims 1 to 5.

7. The granulated product according to Claim 6, wherein the polymer is selected from one or more of a water-soluble synthetic polymer, a natural water-soluble polymer, and a polyol.

8. The granulated product according to Claim 6 or 7, wherein the crosslinking agent is an acid selected from one or more of the following: i) dicarboxylic acids including oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, tartaric acid, tartronic acid, aspartic acid, glutamic acid, fumaric acid, itaconic acid, maleic acid, traumatic acid, camphoric acid, phthalic acid and its derivatives containing at least one boron or chlorine atom, tetrahydrophthalic acid and its derivatives containing at least one chlorine atom, isophthalic acid, terephthalic acid, mesaconic acid, and citraconic acid, ii) tricarboxylic acids including citric acid, tricarballylic acid, 1,2,4-butanetricarboxylic acid, aconitic acid, hemimellitic acid, trimellitic acid, and trimesic acid, iii) tetracarboxylic acids including 1,2,3,4-butanetetracarboxylic acid and pyromellitic acid (iv) polycarboxylic acids such as EDTA, (v) unsaturated carboxylic acids including (meth)acrylic acid, crotonic acid, isocrotonic acid, maleic acid, cinnamic acid, 2-methylmaleic acid, fumaric acid, itaconic acid, 2-methylitaconic acid, α,β-methylene glutaric acid, and monoesters of unsaturated dicarboxylic acids, and vinyl monomers which may be substituted with an alkyl, hydroxyl or sulfonyl group or are styrene substituted with a halogen atom, (meth)acrylonitrile, (meth)acrylamide which may be substituted with a C1-C10 alkyl group, alkyl (meth)acrylate, glycidyl (meth)acrylate, butadiene, and vinyl esters, (vi) inorganic acids such as boric acid and phosphoric acid.

9. The binder is (i) polyvinyl alcohol, or (ii) a reaction product of polyvinyl alcohol and a carboxylic acid (preferably the carboxylic acid is citric acid), the granulated product according to claim 6.

10. An absorbent material comprising the granulated product according to any one of claims 1 to 9, wherein the binder is a cross-linking agent which is a reaction product of a polymer and a cross-linking agent.

11. A method for treating fluid spillage, comprising the step of applying the absorbent material according to claim 10 to the fluid spillage such that the fluid is absorbed by the absorbent material.

12. An animal feed composition comprising the granulated product according to any one of claims 1 to 9.

13. The animal feed composition according to claim 12, wherein the composition further comprises at least one nutrient.

14. The binder is selected from polyvinyl alcohol, bentonite, sodium alginate, potassium alginate, lignosulfonate, urea-formaldehyde, agar, carrageenan, guar gum, cassia gum, xanthan gum, cellulose, gum arabic (acacia), microcrystalline cellulose, methyl cellulose, ethyl cellulose, sorbitan monolaurate, starch or starch derivatives, and combinations thereof, preferably the binder is polyvinyl alcohol, the animal feed composition according to claim 12 or claim 13.

15. A method for preparing the granulated product according to any one of claims 1 to 9, comprising the steps of spray-drying expanded perlite particles with a binder and performing a curing step.

16. The granulated product according to any one of claims 1 to 5, wherein the binder comprises starch or a starch derivative and combinations thereof.

17. The animal feed composition according to claim 14, wherein the binder comprises starch or a starch derivative and combinations thereof.

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