WO2009006377A1 - Granular composites of inorganic particulates and redispersible latex powders and methods - Google Patents

Abstract

A granular composite comprising a) an inorganic particulate, b) a redispersible latex powder, and c) one or more of a superabsorbent polymer (SAP), a porosity-enhancing agent, a water-soluble polymer, an odor control agent, or an oil-absorbing agent and the process of making the same.

Description

GRANULAR COMPOSITES OF INORGANIC PARTICULATES AND REDISPERSIBLE LATEX POWDERS AND METHODS

Field

The present invention relates to granular composites and processes of making the granular composites.

Background Information There is an increasing need for multifunctional granular composite carriers for diverse household products and consumer products and for commercial and industrial applications such as air filters, aqueous liquid absorbent or oil absorbent articles, moisture adsorbent articles, and odor control articles, among others. Developed composite carriers must have good processibility; high absorption capacity of aqueous liquid, moisture, and/or oil; as well as good capability of malodor control and/or volatile organic compound (VOC) control to be effective in various applications mentioned above.

In the past, efforts have been made to solve the problem, but there remains a need for a an effective binder for granular composite carriers with improved properties such as higher moisture or aqueous liquid absorption, oil absorption and retention capacity under various pressures, as well as effective control of malodors and VOCs. It is further desirable that such a carrier provides an effective means to deliver an active ingredient.

Summary

In one embodiment, the present invention provides granular composites comprising a) an inorganic particulate, b) a redispersible latex powder, and c) one or more of a super absorbent polymer (SAP), a porosity-enhancing agent, a water-soluble polymer, an odor control agent, or an oil-absorbing agent.

In another embodiment, the present invention provides methods of making the granular composite. The method includes dry blending of clay, redispersible latex powder, and other ingredients of the composite to form a mixture; wetting the mixture with water or aqueous solution; extruding the wet mixture to form the granular composite; drying the extruded material; and sizing and sieving to form the composite. The method may also include remoisturizing and dedusting the composite. Brief Description of the Drawin2S

Figure 1 is a graph of the effects of different levels of redispersible latex powder (Dow Latex Powder, DLP) and synthetic urine amounts on clump weights.

Detailed Description

In one embodiment, the present invention provides granular composites comprising a) an inorganic particulate, b) a redispersible latex powder, and c) one or more of an SAP, a porosity-enhancing agent, a water-soluble polymer, an odor control agent, or an oil-absorbing agent. The inorganic particulate used in the present invention is a finely divided solid compound of natural or synthetic substance with or without chemical, physical, and/or mechanical surface modification. Various types of inorganic particulates are available and those include, e.g., aluminum hydroxide, aluminum oxide, barium sulphate, borax, calcium silicate, calcium carbonate, calcium phosphate, calcium magnesium carbonate, calcium sulphate, copper (III) hydroxide, copper (II) oxide, iron (III) hydroxide, iron oxide, lithium hydroxide, magnesium borate, magnesium carbonate, magnesium oxide, magnesium phosphate, rubidium hydroxide, sand, silica, fumed silica, sodium bicarbonate, sodium carbonate, talc, titanium dioxide, synthetic and natural zeolites, cancrinites, various types of clay (like bentonites, kaolin, and sepiolites), zinc oxide, and any other water-soluble alkali metal or alkaline-earth metal salts (such as lithium chloride, sulfate, phosphate, and nitrate, sodium and potassium chloride, nitrate, sulfate, sulfonate, percarbonate, peroxide, peroxodisulfate and phosphate, and the like, and further, magnesium chloride and nitrate, calcium chloride, nitrate and sulfate, barium chloride and nitrate and the like).

The inorganic particulate is preferably a metal oxide compound containing one or more metal atoms and one or more oxygen atoms.

In a preferred embodiment of the present invention, the inorganic particulate is clay. Clay is a common name for a number of fine-sized particles in sediment, soil, or rock, and its individual particles are typically smaller than 5 micrometers in diameter. Most clays are composed primarily of clay minerals and these soils contain clays such as kaolinite, smectite, chlorite, and illite. Clays are most commonly formed by surface weathering, for example, by the solution of rocks, such as limestone and by the chemical decomposition of rocks or any of a group of abundant silicates-bearing rock minerals, such as granite and feldspar. Clay consists of a variety of layer silicates, known as phyllosilicate minerals (that are comprised of silicon dioxides, aluminum oxides, and hydroxides) which include variable amounts of structural water. For example, kaolinite, also known as kaolin, consists of a sheet of interconnected silicates combined with a second sheet- like grouping of metallic atoms, oxygen, and hydroxyl, forming a two-layer mineral. Kaolinite most often occurs as plate-like, hexagonally shaped crystals. Kaolin is the preferred clay for the present invention. In another preferred embodiment of the present invention, the inorganic particulate is sodium bentonite clay. There are various synonyms for bentonites, and those include sodium montmorillonite, calcium montmorillonite, saponite, fuller's earth, Wyoming sodium bentonite, swelling bentonite and others. Calcium bentonites are often characterized by much lower swelling and liquid limit values compared to natural sodium bentonite. Natural sodium bentonite comprises sodium as the predominant exchange cation. Sodium bentonite is also known for its ability to swell. It can absorb as many as five to eight times its weight in water. Sodium activated bentonites are produced by the substitution of calcium ions by sodium ions. This transformation can be achieved by the addition of a soluble sodium salt to calcium bentonite. The granular composite of the present invention typically contains at least lwt.% of the inorganic particulates. Preferably, the composite contains more than 20wt.% of the inorganic particulates. More preferably, the composite contains more than 40wt.% of the inorganic particulates. Also, the composite of the present invention typically contains less than 99wt.% of the inorganic particulates. Preferably, the composite contains less than 95wt.% of the inorganic particulates. More preferably, the composite contains less than 80wt.% of the inorganic particulates.

Redispersible latex powders are organic polymer powders made by spray drying of aqueous dispersions containing latex powders. U.S. Patent Publication No. 20060116446, incorporated herein in its entirety by reference, discloses a typical spray drying method and process conditions for the making of redispersible latex powder. During the spray drying process, the redispersible latex powders of the primary particle size of about 0.5 to 2 μm will conglomerate to a size of about 50 to 100 μm in diameter. The increased particle size improves the free flow of the powder and avoids dust formation. Unlike conventional latex powders which have a tendency to coagulate in an uncontrolled and irreversible manner, redispersible latex powder particles will redisperse when contacted with water to disintegrate into a particle size of about 0.5 to 2 μm. Examples of redispersible latex powder used in the present invention include Dow Latex Powder (DLP, made by The Dow Chemical Company). It contains about 75wt.% of dry latex powder, about 12wt.% of polyvinyl alcohol, and about 13wt.% of non-swelling clays, for example, kaolin or other known anti-caking agents. WO 9738042 and US patent publication No. 20020120043, incorporated herein by reference, also illustrate an example of redispersible latex powders that can be used in the present invention.

The composite of the present invention preferably contains at least 0.1wt.% of redispersible latex powder. More preferably, the composite contains more than lwt.% of redispersible latex powder. Typically, the composite contains less than 25wt.% of redispersible latex powder. Preferably, the composite contains less than 15wt.% of redispersible latex powder.

The superabsorbent polymer (SAP) particles used in this invention are ones that absorb many times their own weight in moisture, water, or aqueous liquids. SAP particles swell when they absorb the fluid. SAPs are used in a variety of applications, including diapers, water-barrier applications in the construction industry, and liquid absorbers in food- packaging systems, as well as in hygiene and medical applications. SAP particles can be any of the known hydrophilic polymers that are cross-linked and capable of absorbing large quantities of aqueous fluids, in some instances causing the particle to swell up to several times its dry size. These polymers are well known in the art and are widely available commercially, such as Norsocryl™ (Arkema Group), HySorb™ (BASF AG), Favor™ (Degussa AG), DRYTECH™ (The Dow Chemical Company), K-SAM™ (Kolon Chemical Co. Ltd.), Aqualic™ CA (Nippon Shokubai Ltd.), Sanwet™ (Sanyo Chemical Industries), and Aqua Keep™ (Sumitomo Seika Chemicals). Most SAPs are crosslinked, partially neutralized and/or surface treated. Preferably, the level of crosslinking is selected to give the desired swelling characteristics for the particular application. Examples of some suitable SAPs and processes (including gel polymerization processes) for preparing SAPs are disclosed in US patents 3,669,103; 3,670,731; 3,926,891 ; 3,935,099; 3,997,484; 4,076,663; 4,090,013; 4,093,776; 4,190,562; 4,286,082; 4,340,706; 4,446,261; 4,459,396; 4,654,039; 4,683,274; 4,708,997; 4,857,610; 4,985,518; and 5,145,906, the teachings of all of which are incorporated herein by reference.

The SAPs may be in the form of particles or other forms, such as fibers. The SAPs may also be biodegradable. Preferably, the SAPs are derived from one or more ethylenically unsaturated carboxyl-containing monomers and optionally one or more comonomers copolymerizable with a carboxyl-containing monomer.

Preferred SAPs of the present invention have a centrifuge retention capacity (CRC) as measured in 0.9wt.% NaCl solution via a tea bag method, based on dry weight of said particles, that is less than 70g/g, preferably less than 60g/g, and more preferably less than 50g/g. Preferred SAPs of the present invention have a CRC as measured in 0.9wt.% NaCl solution, based on dry weight of said particles, that is greater than about 7g/g, preferably greater than about 10g/g, and more preferably greater than about 15g/g.

Preferred SAPs of the present invention have an absorption under load (AUL) as measured in 0.9wt.% NaCl solution and under pressure of 0.3psi that, based on the dry weight of said particles, is less than 50g/g, preferably less than 40g/g, and more preferably less than about 30g/g; it is greater than 5g/g, preferably greater than 7g/g, and more preferably greater than 10g/g.

Preferred SAPs of the present invention have a dry-basis size, as measured by sieve analysis that is less than 1000 microns, preferably less than 800 microns, and more preferably less than 500 microns, and that is greater than 0.1 microns, preferably greater than 10 microns, more preferably greater than 100 microns, and most preferably greater than 150 microns.

The composite of the present invention preferably contains at least 0.1wt.% of SAP. More preferably, the composite contains more than lwt.% of SAP. Typically, the composite contains less than 99wt.% of SAP. Preferably, the composite contains less than 50wt.% of SAP.

The composite of the present invention has a granular structure that can be designed to show higher porosities, which is beneficial for fast uptake of fluids when contacted with water, aqueous solutions, and moisture or gases in the air stream. The degree of porosity of the composite granule can be controlled by the types, shapes and amounts of the porosity- enhancing agent, and the homogeneity of the distribution of the porosity-enhancing agent in the composite granule matrix.

In principal, there are different classes of substances that can improve the porosities of the composite structure. These include various types of thermoplastic or thermoset polymer micro- spheres; highly crosslinked polymer beads with or without inner porosities; and water- insoluble inorganic or organic particulate substances of nano-, submicron-, or micron-sized particles like glass beads or glass micro-spheres, precipitated silica, silicon dioxide, fumed silicas, magadiite and modified magadiite, titanium dioxide, aluminum oxide, magnesium dioxide, zinc dioxide, talc, calcium carbonate, ground corn, ground rice, ground barley, cellulosics, starch, carbon tubes, metal particles or metal micro-spheres, polymer fibers, natural fibers, among others.

The porosity-enhancing agents of inorganic or organic nature can assume the morphology of platelets, tubes of different characteristic length, e.g., nano-carbon tubes, cylinders, polycylinders, spheres, and balls e.g., fullerene types, polyhedrals, discs, needles, polyneedles, cubes, irregular shapes, ellipsoids, among others.

The porosity-enhancing agent is used preferably less than 40wt.% and more preferably less than 20wt.%, and most preferably less than 10wt.%, all based on the weight of the composite granule. Prior to use, the porosity-enhancing agent can be subjected to treatments, for example, surface treatments.

Preferred porosity-enhancing agents are polymer micro-spheres and glass microspheres. Typically, the more preferred polymer porosity-enhancing agent is PERGOP AK® HP (CAS No. : 9011-05-6, Trademark of Albemarle Corporation, Baton Rouge, Louisiana, USA). PERGOPAK agent is a polymethyl urea resin, containing a small quantity of free, reactive methylol groups (approximately 0.6%), which seems additionally useful for better crosslinking in the matrix. PERGOPAK agent is typically an agglomerate of 3.5 - 6.5 μm diameter on average formed by primary particles of 0.1 - 0.15 μm diameter.

Water-soluble polymers and copolymers used in the present invention represent a diverse class of macromolecules including naturally occurring polymers such as polysaccharides, and biopolymers such as polypeptides and proteins and various types of synthetic polymers, copolymers and block copolymers. (See "Water Soluble Polymers," Encyclopedia of Polymer Science and Technology, John Wiley & Sons, Inc., Eds. Charles L. McCormick, Andrew B. Lowe, Neil Ayres) Preferred naturally occurring water-soluble polymers include, for example, polynucleotides, polypeptides, proteins, enzymes, and polysaccharides. Commercially, polysaccharides have traditionally been obtained from renewable resources in plants and animals. Also, microbial sources have produced commercially useful polysaccharides such as dextran and xanthan. Water-soluble polysaccharides include starch and starch derivatives, glycogen, glucans, alginic acid, carrageenan, pectins, plant gums, e.g., gum Arabic, hyaluronic acid, and synthetically modified polysaccharides.

More preferred water-soluble polymers are synthetically modified polysaccharides. Water solubility can be bestowed on a number of naturally occurring polysaccharides by modification producing charged or polar functionality. Typical synthetically modified polysaccharides are cellulose derivatives including carboxymethylcellulose (CMC), or its monovalent metal or ammonium salts, hydroxyethylcellulose (HEC) and hydroxypropylcellulose (HPC), methylcellulose, hydroxypropylmethylcellulose (HPMC), cellulose sulfates and phosphates, and chitin derivatives and chitosan. Examples of the preferred synthetically modified polys accharide-basis water-soluble polymers are WALOCEL™ C and WALOCEL™ CRT carboxymethyl cellulose, CELLOSIZE™ hydroxyethyl cellulose, and METHOCEL™ cellulose ethers (commercially available from The Dow Chemical Company). The most preferred water-soluble polymers are the METHOCEL™ cellulose ethers which are water-soluble methylcellulose and hydroxypropyl methylcellulose polymers.

A number of commercially available nonionic synthetic water-soluble polymers and copolymers are available, and they include, for example, polyacrylamide, poly(ethylene oxide) such as POLYOX™ (commercially available from The Dow Chemical Company), poly(vinyl alcohol), poly(methyl vinyl ether), and poly(N-vinylpyrrolidinone).

Other preferred water-soluble polymers are polyelectrolytes that are polymers with charged functional groups attached along the chain. These polymers are usually classified as either poly anions or polycations. Preferred anionic water-soluble polymers are poly (aery lie acid) and its salts, poly(methacrylic acid) and its salts, poly(vinylsulfonic acid) and its salts, poly(styrenesulfonic acid) and its salts, poly(2-sulfoethyl methacrylate), poly(3-sulfo-2- hydroxypropyl methacrylate), and poly(2-acrylamido-2-methylpropanesulfonic acid).

Examples of preferred water-soluble polymers that can be employed in the present invention include polycationic water-soluble polymers that are a linear polyelectrolyte with a cationic charge density. Examples of water-soluble cationic polymers are poly(2- (dimethylamino)ethyl methacrylate), poly(2-dimethylamino ethyl methacrylate), poly(N-[3- (dimethylamino)propyl] methacrylamide), polydiallyldimethylammonium chlorides, polyvinylpyridines, poly(4-vinylaniline), poly(ethylene imine), polyvinylamine, cationic hydroxyethyl cellulose, (for example, UCARE JR-09, JR-400, LR-400 and JR-30M from Amerchol Corporation, USA), and a chiosonium pyrrolidone carboxylate (available commercially as KYTAMER PC from Amerchol Corporation), and the like.

The solubility of preferred water-soluble polymers advantageously is such that at least 0.05 gram, preferably at least 1 gram, and more preferably at least 2 grams, of water-soluble polymer is soluble in 100 grams of de-ionized water at room temperature and one atmosphere. Water-soluble polymers having a wide range of molecular weights are suitable for use in the present invention. Preferably, the water-soluble polymer has an average molecular weight ranging from 500 to 10,000,000 grams per mole, more preferably from 2,000 to 2,000,000 grams per mole, and most preferably from 50,000 to 500,000 grams per mole. Methods for determining the weight average molecular weight of water-soluble polymers are well known in the art. For the purposes of the present invention, weight average molecular weight is determined using gel permeation chromatography.

In a preferred embodiment, the water-soluble polymer preferably is added as a powder. The water-soluble polymer is preferably used in an amount from 0.01 to 25wt.%, more preferably from 0.5 to 10wt.%, and most preferably from 1 to 5wt.%, based on the total weight of dry mixture. Mixtures of water-soluble polymers of different types can be employed. The water-soluble polymer is added as a powder simultaneously with, prior to, or after the blend of the inorganic particulate, redispersible latex powder, SAP, odor control agents and other powder form additives. Oil-absorbing polymers are known in the art. Many of such polymers are capable of absorbing many times their original volume of oil or organic liquid. The term "oil-absorbing polymer" as used herein refers to those polymers having the property of being substantially insoluble in, but capable of absorbing (being swollen by), one or more oils or organic liquids such as natural oils (from canola, castor, corn, cottonseed, olive, rapeseed, soybean, sunflower, other vegetable and animal oils, and sebum), fragrances, gasolines, diesel fuels, lubricating oils, kerosenes, light oils, heavy oils, aromatic solvents (such as benzene, toluene and xylene), and various chlorinated solvents (such as chloroform, carbon tetrachloride and the like), monoglycerides, triglycerides and the like. A variety of compositions are employed to prepare such oil-absorbing polymer particles, and various oil-absorbing polymer particles are taught in the following U.S. Patent Nos. 3,520,806; 3,686,827; 3,750,688; 3,881,295; 3,958,590; 3,999,653; 4,024,882; 4,019,628; 4,130,400; 4,172,031; 4,529,656; 5,628,110; 5,677,407; 5,712,358; 5,777,054; and 5,834,577. The teachings of these are incorporated herein by reference.

Preferred oil-absorbing polymers of the present invention are a crosslinked copolymer comprising 100 to 55wt.% isobornyl methacrylate and about 0 to 45wt.% of a polymerizable vinyl comonomer. An example of such a comonomer is the alkylstyrenes or the alkyl esters derived from Ci to C₂₄ alcohols and acrylic or methacrylic acids or mixtures thereof. The alkyl styrenes have alkyl groups containing from 4 to 20 carbon atoms and preferably from 4 to 12 carbon atoms. Such alkylstyrenes include tertiary alkylstrene including p-tert- butylstrene, p-tert-amylstyrene, p-tert-hexylstyrene, p-tert-octylstyrene, p-tert- dodecylstyrene,p-tert-octadecylstyrene, and p-tert-eicosylstyrene; n-alkykstysyrene, n- butylstyrene, n-dodecylstyrene, n-octadecylstyrene, and n-eicosylstyrene; sec-alkystyrene, including for example, sec-butylstyrene, sec-hexylstrene, sec-octlstyrene, sec-dodecylstyrene, sec-octadecylstyrene, and sec-eicosylstyrene; isoalkylstyrene, including for example, isobutylstyrene, isoamylstyrene, isohexystyrene, isooctylstyrene, isododecylstyrene, isooctadecylstyrene, and isoeicosylstyrene; and copolymers thereof. The alkyl esters derived from Ci to C₂₄ alcohols and acrylic or methacrylic acids include hexyl acrylate, hexyl methacrylate, octylacrylate, octyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl methacrylate, laurylmethacrylate, dodecyl acrylate, lauryl acrylate, eicosyl acrylate, eicosylmethacrylate, or mixtures thereof. Preferably, the oil-absorbing polymer particles of the present invention are the crosslinked copolymers from 100 percent to about 55wt.% of isobornyl methacrylate and from 0 percent to 45wt.% of laurylmethacrylate.

The degree of oil absorption (swelling capacity) is dependent primarily upon the amount of crosslinking present in the polymer particles. The quantity of crosslinking agent utilized should be sufficient to permit an absorption (swelling) of the polymer particles when exposed to the organic oily liquid and sufficient to prevent dissolution of the particles by the oily liquid. Normally such crosslinking agents are employed in the range from 0.5 to about 2wt.% based on the total weight of the monomer or monomers. Generally, the level of crosslinking agent is less than 1 percent which permits the polymers to swell easily and imbibe a substantial volume of organic liquid. Crosslinking agents which can be used in preparing the absorbing polymers suitable for use in the present invention include polyethylenically unsaturated compounds such as divinylbenzene, diethyleneglycol dimethacrylate, as well as any other di- or poly-functional compound known to be of use as a crosslinking agent in polymeric vinyl-additional compositions. The preferred crosslinking agent is divinylbenzene.

The degree of oil absorption is typically measured using a dry oil-absorbing polymer where the polymer particles are allowed to soak in liquid oil (for example, canola oil) while additional oil was introduced in portion gradually until free liquid oil was noticeable, and then the oil uptake could be calculated in grams of oil per gram of dry oil-absorbing polymer (g/g) as follows. Oil uptake (g/g) = (amount oil added in grams / amount polymer in grams). Preferred oil-absorbing polymer particles of the present invention have an oil uptake as measured in canola oil (based on dry weight of oil-absorbing polymer particles); is less than 40g/g, preferably less than 30g/g, and more preferably less than 20g/g; and is greater than lg/g, preferably greater than 3g/g, and more preferably greater than 5g/g.

In a preferred embodiment, the oil-absorbing polymer preferably is added as a powder. The oil-absorbing polymer is preferably used in an amount of from 0.01 to 50wt.%, more preferably from 0.5 to 25wt.%, and most preferably from 1 to 15wt.%, based on the total weight of dry granular composite. Mixtures of oil-absorbing polymers of different types can be employed. The oil-absorbing polymer is added as a powder simultaneously with, prior to, or after the blend of the inorganic particulate, redispersible latex powder, SAP, odor control agent and other powder form additives.

The odor control agent used in the present invention may include one or more of an activated carbon such as powdered, granulated, or extruded activated carbon; a cyclodextrin; a porous polymer adsorbent; an ion exchange polymer; sodium bicarbonate; borax; a peroxide such as sodium, potassium or ammonium percarbonate, peroxide and peroxodisulfate a permanganate such as sodium or potassium permanganate; a biocide; a plant extract such as extract and/or dry powder of green tea leaves, olive leaves, yucca, aloe, and Quillaja; citric acid; chelating agents; natural and synthetic zeolites; perfumes; various metals and metal compounds, including copper sulfate, copper acetate, zinc sulfate, zinc chloride, zinc ricinoleate, metallic or ionic silver in various forms (such as colloidal silver nano-particles, silver acetate, silver nitrate and silver thiosulfate complexes), a zeolite powder ion exchanged with silver, copper and/or zinc ions; chitosan, or a mixture thereof. In a preferred embodiment, the powdery odor control agent preferably is added as a powder and the soluble metal salts as an aqueous solution. The powdery odor control agent is preferably used in an amount from 0.01 to 50wt.%, more preferably from 0.5 to 25wt.%, and most preferably from 1 to 15wt.%, based on the total weight of the dry granular composite. The soluble metal salt-type odor control agent such alkali metal salts of chelating agent, copper sulfate, copper acetate, zinc sulfate, zinc chloride, zinc ricinoleate, metallic or ionic silver in various forms (such as colloidal silver nano-particles, silver acetate, silver nitrate or silver thiosulfate complexes) is preferably used in an amount from 0.0001 to 15wt.%, more preferably from 0.0025 to 10wt.%, and most preferably from 0.05 to 5wt.%, based on the total weight of dry granular composite. Mixtures of powdery odor control agents of different types can be employed. The powdery odor control agent is added as a powder simultaneously with, prior to, or after the blend of the inorganic particulate, redispersible latex powder, SAP, oil-absorbing polymer and other powder form additives. The metal salt odor control agent is added typically as an aqueous solution during the wetting of the inorganic particulate, redispersible latex powder, SAP, oil-absorbing polymer, and other powder form additives. The present invention also provides a process of making the granular composite as described below.

The process involves dry blending powdery ingredients of the composite to first form a mixture. It is preferred to add the various powder ingredients such as inorganic particulate, SAP, oil-absorbing polymer, and porosity-enhancing agent to the dry blender (mechanical agitation equipment with horizontal or vertical rotary blades and optionally with nozzles and heating, such as a Loedige blender, Forberg blender, Hobat blender, or V-shaped blender or fluidized bed). According to the preferred process for the preparation of granular composites, the free-flowing powdery ingredients can be added to the blender during the process at any time and in any sequence. The powdery ingredients are blended homogeneously before the extrusion process starts.

After the powdery ingredients are blended homogeneously, the dry mixture is then wetted with water or aqueous solution by spraying. During wetting, the dry mixture generally absorbs all of the water or the aqueous solution to form a wetted mixture. The term "wetted mixture" refers to a moistened blend comprising inorganic particulate, for example, bentonite-type clay, partially swollen SAP, and/or partially hydrated water-soluble polymer particles, and/or oil-absorbing polymer particles, and/or other ingredients of the present invention. Preferably, the wetted mixture comprises 5 to 500 percent by water (as determined by weight loss after drying the wetted mixture at above 100⁰C. for at least an hour). The wetted mixture is preferably processed into an agglomerated, particulate shape during the wetting process in the blender in order to facilitate the homogeneous mixing of the blend material and water. Particle sizes of the wetted material range preferably from 0.01 to 10cm. More preferably, particle sizes of the wetted material range from 0.05 to 5cm and most preferably from 0.1 to 2.5cm. Prior to extrusion, the moisture content of the wetted material particles may be adjusted by drying and/or microwaving or by means commonly known in the art of removing water present in the wetted material.

The extrusion process of the wetted material is performed in an extrusion device comprising a die and mandrel by forcing the wetted material through the extrusion device and out of an orifice as an extrudate. The preferred extruder is a Nica low-pressure basket extruder, Shugi low-pressure basket extruder, single-screw extruder or twin-screw extruder type. The die hole diameter is preferably 2 cm or less and more preferably 1 cm or less. Preferably, the die has a hole diameter of 0.02cm or greater, and more preferably 0. lcm or greater. The die hole can be any shape such as circular, ellipsoidal, square, triangular, etc. The temperature at which the extrusion takes place can be adjusted such that liquid (including water) is removed in a reasonable time period, so as to sufficiently reduce the following drying time or even avoid further drying of the extruded wet composite material. Preferably, the temperature of the wet material during extrusion is 8O⁰C or less, preferably 5O⁰C or less and more preferably 1O⁰C or above. To extrude the wetted composite material, a die with any size hole diameter can be used. During extrusion, an additional lubricant such as polyethylene oxide-type polymers, for example, POLY OX™ (commercially available from The Dow Chemical Company), or surfactants can be used in a powder form or solution form in amounts ranging from 0.01wt.% to 5wt.%, based on the total wet material. The extruded wet material shows angel hair pasta-like consistency and can have any length. Preferably, the extruded wet paste has a length of lcm or greater, and more preferably 5 cm or greater. In a general terms, the characteristic length of the extruded wet pasta, i.e., the ratio of the length to the diameter (or thickness) of the wet paste is 10 or greater, preferably 50 or greater, and more preferably 100 or greater.

After extrusion, the wet composite pastes are subjected to drying conditions to remove or reduce the water. Typically, the moisture content of the dried composite is between zero and 20wt.%, preferably between 5 and 10 wt.%. The temperature at which the drying takes place is a temperature high enough that the water is removed in a reasonable time period, yet not so high as to cause degradation of the polymeric ingredients in the granular composite particles. Preferably, the temperature of the resin particles during drying is 25O⁰C or less, and more preferably 18O⁰C or less. Desirably, the temperature during drying is 5O⁰C or above, preferably 8O⁰C or above and more preferably 100⁰C or above. The drying time should be sufficient to remove substantially all of the water and optional lubricant solvent. Preferably, the minimum drying time is 5minutes or greater, with 15minutes or greater being preferred. Preferably, the drying time is 24 hours or less, more preferably 12 hours or less, and most preferably 3 hours or less. In a preferred embodiment, the drying occurs in dryers where heated air or inert gas is blown through or over layers of the extruded wet materials (extrudates). Suitable drying means include fluidized bed driers, rotary driers, forced air ovens, tray driers, or drum driers. Preferred dryers are fluidized beds or belt dryers. The final particle size of the granular composite particles is obtained after the sizing and sieving process. Preferably, the particle size reduction is performed by using a conventional mechanical means of particle size reduction, such as grinding, chopping, and/or cutting. The object is to reduce the particle size of the granules to a particle size acceptable in the end use. In a preferred embodiment, the composite particles are chopped and then ground. The final particle size is preferably 2 cm or less, and more preferably 1 cm or less. Preferably the particles have a size of 0.01 cm or greater, and more preferably 0.03 cm or greater. In general terms, the characteristic length of the final particle size, i.e., the ratio of length to diameter (or thickness) is 50 or less, preferably 20 or less, and more preferably 5 or less. Most preferably the characteristic length of the final particles is 1 or greater. After sizing, the composite particles may be difficult to handle due to static electricity. It may be desirable to remoisturize the particles to reduce or eliminate the effect of the static electricity. In a preferred mode, the dry particles are contacted with a sufficient amount of water vapor or fine droplets of water to reduce or eliminate the effects of the static electricity, yet not so much so as to cause the particles to agglomerate. In this process, the dry particles are moisturized with 0.5wt.% or more by weight of water and more preferably 1 percent or more by weight of water. Preferably, the dry particles are humidified with 10 wt.% or less of water and more preferably 7wt.% or less of water. Optionally, agglomeration prevention additives (anti-caking agents) may be added to the composite particles. Such anti- caking additives are well known in the art and include surfactants and inert inorganic particles such as silica.

During such sizing as described above, dust (characterized by extremely small particle sizes) may result, for example, particle sizes less than or equal to 10 microns. The amount of dust generated will vary based on manufacturing procedures. To reduce levels of unassociated dust and to inhibit the production of unassociated dust during handling of the composite material, the dried granule particles can be contacted with an effective amount of a dust control agent. The dust control agent (dedusting agent) serves to adhere the dust together into larger clusters, to the larger granular composite particles, or to the walls of the mixing vessel or container in which the composite particle is retained during handling, all of which will translate to reduced levels of unassociated dust in the finished polymer product at the various stages of handling. Moreover, the application of the dust control agent to the granular composite particles does not substantially affect the performance or properties of the composite particles in any detrimental way.

Preferred dust control agents are either hydrophobic or hydrophilic materials. Exemplary hydrophobic dust control agents may include aliphatic hydrocarbon oils, such as mineral oil, alkanes or alkenes having between approximately 7 and 18 carbon atoms, natural oils (such as corn, olive, rapeseed, soybean, sunflower, other vegetable and animal oils), as well as silicone oils. The above compounds may be employed in solutions, in mixtures, or in emulsions. Generally, the amount is at least 100, preferably at least 200, and more preferably at least 300 ppm based on the weight of the polymer particles. The amount is less than 6000, preferably less than 3000, and more preferably less than 1000 ppm based on the weight of the composite particles.

Exemplary hydrophilic dust control agents may include water-soluble polymers such as a propoxylated polyol (available from The Dow Chemical Company under the brand name VORANOL). Examples of preferred dust control agents are also polycationic water-soluble polymers such as polydiallyldimethylammonium chlorides, cationic hydroxyethyl cellulose, for example, UCARE JR-09, JR-400, LR-400, JR-30M and KYTAMER PC (Amerchol Corporation, USA) and the like. The polycationic water-soluble polymer is used in an amount from 500 to 2,500 ppm, based on the weight of the dry composite granule. The concentration of the propoxylated polyol in water ranges preferably ranges from 0.1 to 10wt.% and more preferably from 1 to 5wt.%.

Typically, the composite of the present invention contains at least O.lwt.% of one or more of an SAP, a porosity-enhancing agent, a water-soluble polymer, an odor control agent, or an oil-absorbing agent. Preferably, the composite of the present invention contains more than 0.1 but less than 99wt.% of one or more of the following: an SAP, a porosity-enhancing agent, a water-soluble polymer, an odor control agent, or an oil-absorbing agent. More preferably, the composite of the present invention contains more than 1 but less than 50wt.% of one or more of an SAP, a porosity-enhancing agent, a water-soluble polymer, an odor control agent, or an oil-absorbing agent.

In one preferred embodiment, the present invention provides a granular composite comprising clay and redispersible latex powder, wherein the composite comprises more than 15wt.% of clay based on the combined weight of the clay and the redispersible latex powder. The composite of the present invention may, depending on specific applications, further comprise a fragrance agent, a surfactant, a pigment, a colorant, a moisture-reactive indicator, a pH indicator, or a mixture thereof.

In another preferred embodiment, the present invention provides a granular composite comprising a) 1 to 99wt.% of clay, b) 0.1 to 25.0wt.% of redispersible latex powder, c) 0.1 - 99wt.% SAP, d) 0.1 - 25wt.% water-soluble polymer, e) 0.01 - 25wt.% porosity-enhancing agent; f) 0.01 - 25wt.% odor control agents; and g) 0.01 - 25wt.% water.

Optionally and depending on different demands of different applications, the composite may also include from 0.01 % to 25wt.% of one or more low volatile organic humectants such as glycerine, propylene glycol, sorbitol, xylitol and maltitol, dextrose, citric acid, lactic acid, or urea; from 0.01% to 5wt.% of one or more additional fragrances; from 0.01% to 5wt.% of one or more anionic, cationic, and/or non-ionic and/or amphoteric surfactants, such as alkali metal alkylsulfates, alkylether sulfates, alkylarylsulfonates, alkyl sulfonates, fatty acids, or quaternary ammonium, imidazolinium, morpholinium, or linear/ branched alkoxylated alcohols, alkoxylated alkylphenols, alkoxylatedglycosides, or alkylpropylamidoalkylbetaines; from 0.001% to 5wt.% of one or more of the colorants; from 0.001 to 5 wt. % of one or more pigments; from 0.01 to 5 wt.% of one or more moisture reactive indicators such as a dehydrated transition metal salt containing one of more of the metal ions like Cr³⁺, Fe²⁺, Co²⁺, Ni²⁺, or Cu²⁺; from 0.001 to 5wt.% of one or more enzymes or encapsulated enzymes; and/or from 0.01 to 2wt.% of one or more pH indicators. The present granular composite represents a multifunctional granular composite and can be used in many different applications. Following are some non-limiting examples of applications using the present granular composite.

The present granular composition may be used in air filter products for odor control in typical households, schools, offices, commercial buildings, public bathrooms, restaurants, hospitals, assisted living and nursing homes, as well as in commercial applications such as cabin air filtration/freshening applications for VOCs such as automobiles, aircraft, buses, trains, trucks, RVs, ships, and boats.

The granular composite particles of this invention can be used in any application which desires absorption of aqueous fluids (such as water, urine, and blood) or reduction of malodors and/or odorous volatile organic compounds (VOCs) and/or absorption of oily substances.

The present granular composite may also be used in absorbent cores, cat litters, and personal care applications in baby diapers, adult incontinence products, and feminine care products. The present granular composite may also be used in various health- and hygiene- related applications like wound dressings and fabrics, ostomy/colostomy bags, hospital gowns, blood pads, surgical face masks, wound dressings, and bed pads.

The present granular composite may also be used for body bags and dead animal containment as well as for food packaging applications for meat, fruits, and poultry. It may also be used in building applications such as natural mineral or synthetic insulation wool, mortar, cement, and concrete.

The present granular composite may also be used in gardening applications in moisture control and triggered release of actives of moisture, fertilizers, pesticides, herbicides, fungicides, and biocides. The present granular composite may also be used in agricultural and horticultural applications (such as in livestock odor containment) and in consumer malodor product applications such as in malodors for bathroom odors, pet odors, cooking odors, fridge odors, furniture and closet deodorizers, carpet deodorizers, kitchen garbage bags, footwear, perspiration, on clothing, diaper pails, soiled laundry and laundry bags, trash containers, smoke eaters, sportswear, firemen's clothes, meat and fish trays, and carpet backing.

The present granular composite may also be used in industrial applications such as catalysts, food processing, waste processing, landfills, water filtrations, wildfire control, and paper and pulp manufacturing.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent.

The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting of the remainder of the disclosure in any way whatsoever.

Examples

The following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Procedure for the Preparation of Granular Composite Samples

A. Blend Materials

Sodium bentonite (CAS Number: 1302-78-9) was obtained from Black Hills Bentonite, LLC (Mills, WY) and used as obtained. The sodium bentonite clay used in this work is normally ground to 75-80% minus 200mesh (<0.074mm or 74 microns). Redispersible Latex Powder - Different types of Dow redispersible latex polymer powders (Dow Latex Powder, termed "DLP" hereafter) are commercially available. In this example, DLP 220, which is a vinylacetate/ethylene-copolymer having a glass transition temperature (T_g) of -2⁰C and a minimum film forming temperature (Mf⁷FT) of O⁰C, was used throughout the experiments. The DLP powder levels varied from 0 to 2.5 to 5wt.%, based on the weight of total dry blend material.

Superabsorbent Polymer (SAP) Material - Fine-sized SAP material (DRYTECH™ STlO fines, termed "fines" hereafter) were obtained from the DRYTECH Midland SAP plant and used throughout the experiments. Typical particle sizes of the fines employed in the experiments are much smaller than 300 microns. In one experiment, regular DRYTECH STlO SAP was used with a full cut-size fraction approximately between 100 and 850 microns.

Addition of PERGOPAK™ M - PERGOPAK™ M (Trademark of Albemarle Corporation, Baton Rouge, LA) was added to the bentonite blend material at 5wt.%. PERGOPAK M is a polymethyl urea resin (urea-formaldehyde-condensation product) containing a small quantity of free methylol groups (0.6%) and was used as obtained (CAS No. : 9011-05-6).

B. Blending

All material was then put into a large, sealed plastic bag and hand-shaken for 3-5 minutes until all materials were visibly incorporated uniformly.

C. Wetting Material for Extrusion An amount of 2 kg of the material was put into a 16 x 24" plastic pan so that the material was evenly distributed to a depth of about ³A". Water was added to the material up to 1: 1 weight ratio by pre- weighing deionized, room temperature water. The water was applied by a compressed air sprayer fitted with an 8004 flat-fan nozzle at 25 psi. The surface was sprayed uniformly to the point of uniform wetting, not allowing any visible pooling of the water. The material was then mixed by hand in the pan to incorporate the wetted material with the dry layer below. The spraying/hand mixing process was repeated until the entire volume of water was incorporated into the dry material. The finished product resulted in an agglomerated, pea-sized (or smaller) material. If the material was over-mixed or over- handled, it resulted in a much stickier, larger agglomeration that did not extrude smoothly. The material was covered with poly sheeting and allowed to set for approximately 30 minutes to allow equilibration prior to extrusion.

D. Extrusion

The wetted material was extruded using a Nica low-pressure basket extruder (Nica E140 extruder, Aeromatic -Fielder. Ltd., Eastleigh, Hants, UK) with a 1.2mm sized screen. The material was added all at once to the basket. The material extruded well with long, angel hair pasta-like consistency. The material was collected and carefully put onto nylon screen- covered stainless steel drying trays approximately 1" deep, which were then placed in a drying oven. Extruded particles were compressed gently to ensure even drying. Unless otherwise stated, this extruder was used throughout the experiments.

E. Drying

The extruded material was placed gently on drying trays to ensure even drying and then into the tray drier set at 55⁰C overnight. The product was then carefully fluffed to assist and expedite drying. The total drying time was approximately 24 hrs. The average moisture was approximately 7wt.% (drying in a 105⁰C oven for 12 hrs).

F. Sieving

The dried material was then broken up and placed into a Glatt sieve fitted with a 2mm herringbone -patterned screen and captured into plastic bags. The material broke up well with very little dust observed during the process. This material is termed granular composite "type A" hereafter and has an approximate diameter of lmm with lengths ranging from about lmm to about 15mm.

G. Grinding

In some cases, the granular composite particles obtained after the sizing and sieving process were additionally ground using a household coffee grinder. The grinding of the composite granules was performed to reduce the particle length, creating shorter particles with the same diameter. After grinding, the small size fraction passing through the sieve (lOOmesh or 150microns) was discarded. The resulting larger particles were retained and measured and found to have a narrow particle size distribution with a mean and median of 1090μm and 1066μm respectively. The material is termed granular composite "type B" hereafter. Table 1 shows the particle sizes and distribution for the composite granules after grinding and sieving with a lOOmesh size sieve, measured using an LS particle size analyzer (Beckman Coulter LS 13 320).

Table 1: Particle Sizes of Ground Granular Composite (Type B)

Testing Procedures for the Properties of Samples

Absorption Testing: Centrifuge Retention Capacity (CRC) Procedure

An amount of 300 mg of granular composite (type A) were placed within a heat sealable tea bag. The tea bag was 59mm by 75mm (Grade 7291, available from Ahlstrom Fiber Composites, Chirnside, Dunes Berwickshire, Scotland). An iron was used to heat-seal the edges so that the bag was completely closed. The granular composite particles were distributed evenly throughout the bag by holding it horizontally and tapping it gently. A 0.9% saline solution was poured into a glass tray with approximate dimensions of 30cm x 19cm x 5cm. The tea bag was immersed for 1 hour in the saline solution. The tea bag was then removed from the solution and centrifuged at lόOOrpm for 3minutes. Then the tea bag was weighed. The weight of the saline absorbed was determined by the difference in the original weight of the tea bag with the dry pellets and the weight of the wet tea bag and wet pellets after they were centrifuged. The weight ratio of the saline solution absorbed to the weight of dry granular composite particles was the centrifuge retention capacity (CRC), and it was recorded in grams of solution per gram of dry granular composite particles (g/g). Absorption Testing: Absorbency Under Load (AUL) Procedure An amount of 400mg of granular composite sample was spread out evenly in the bottom of an "AUL cell". This was a hollow plastic cylinder, 31mm diameter on the outer edge of the plastic and 25mm diameter on the inside. The cell was 33mm high. The bottom end of the cell was covered by a fine nylon mesh. After the composite particles had been added, a plastic piston was placed on top of the pellets. The weight of the cell with the pellets and the piston was recorded. Then, a lOOg weight was placed in the cell on top of the piston. The combined weight of the lOOg weight and the piston was 109.4g, giving a 2.IkPa (0.3psi) load on the particles. An assay tray (24cm x 24cm x 2.5cm) was used, with 6 holes drilled in the cover. The holes had a diameter of 31mm with a circular orientation. The six holes were circumscribable by a 124mm diameter circle. The cover was then removed and a glass fritz (124mm diameter, 12mm height) was placed inside the tray, and positioned under the 6 holes in the tray cover. A 0.9% saline solution was added into the tray until the level was even with the top of the fritz, without covering it. A 124mm diameter piece of filter paper was then placed on top of the fritz. If done correctly, the saline solution wicks through the fritz and wets the filter paper. The tray cover was then placed on top of the tray. The AUL cells were then placed through the drilled holes so they rested on top of the filter paper on top of the fritz. The cells were then added two at a time and placed opposite each other. The pellets were then given two hours to absorb the solution. After one hour, the cells were removed from the tray. The lOOg weights were then removed from the cells, and the cells were weighed. The difference between the wet weight and the dry weight of the cells gave the mass of the solution absorbed by the composite particles. That number was divided by the original mass of the granular composite particles to give the AUL in g/g. Clumping Absorption Testing Procedure

One 2.5x2 inch plastic hexagonal weigh boat was labeled. About 20 grams of composite granule material was placed into the corresponding weigh boat. Each granule sample was dosed with 2mL (approx. 2 grams) of synthetic urine (made with 2.ImL of 28% aqueous ammonia, 50.4g of urea, 4.3g of CaCl₂*2H₂θ, and 50OmL of water). A wait time of 1 hour was given for urine to be absorbed and a clump to form. After the wait time, each sample was placed individually on a laboratory balance and the balance was zeroed. The clump was removed gently using a spatula. The weight loss was recorded on the balance as the clump weight. Finally, the length, width, and depth of each clump were recorded in millimeters. Based on the experiment above, the clumping absorption in grams of synthetic urine solution per gram of dry granular composite particles can be calculated as follows. Clumping absorption (g/g) = 2 g/(clump weight - 2) g. The clumping absorption is a measure of efficacy of granular composite particles to absorb liquids upon the brief contact with liquid. A lower clump weight (g) results in a higher clumping absorption (g/g). For simplicity, the clump weight (g) is used throughout the examples in the present invention. Odor Control Efficacy Testing

Two different methods were used for evaluating odor control efficacy: a sniff test and gas chromatography (GC). Sniff Testing

An amount of 30g of composite granules was added to a 10OmL glass bottle. The testing solution was prepared by adding 800 ppm trimethyl amine (TMA) to the synthetic urine above. Each litter sample was dosed with 2mL urine/TMA solution. Sniff testing was performed at specified intervals at room temperature using the following scores.

0= non-malodorous; 1 = slightly malodorous; 2 = malodorous; 3 = strongly malodorous Gas Chromatography (GC) Measurement

In some cases, the efficacies of the granular composite for controlling malodors and volatile organic compounds (VOCs) were measured using TMA, dimethyl disulfide (DMDS), formaldehyde, styrene monomer, and dimethylphthalate (DMP).

General Procedure for Preparing Vials Vials were prepared by weighing 0.1 g of granular composite particles into a 22 mL headspace vial. The granular composite of type A was used throughout the GC experiments. Then, a 2mL vial was lowered into the headspace vial. After that, typically lμL of solution was added to the 2mL vial. Next, the headspace vial was capped. This procedure precluded any liquid contact between the solution and the granular composite particles. Any interaction could only have been from vapor. The vials sat at room temperature for several hours before being sampled. The analyte in the headspace was detected by GC with either mass spectrometry (MS) or flame ionization detection (FID).

The solution composition used with each compound is given in Table 2.

Table 2: Specifics for Each Compound

The conditions for each of the four compounds are given below.

Table 3: Instrument Conditions for TMA, Formaldehyde, and DMP

Table 4: Instrument Conditions for DMDS and styrene:

Large Container Malodor Testing

A one-gallon cylindrical plastic container (9 VA" tall, 5 VA" diameter) was used as the testing apparatus. An aluminum fitting (dimensions: ring - outside diameter 1 1/8", inside diameter Vi"; fitting - outside diameter 1 1/8", thread diameter Vi", outside tubing connection diameter 5/16"; inside diameter VA" , height 1 VA" , thread height Vi") was installed on a corresponding lid with a Vi" hole cut into the lid. The fitting was tightened securely with fingers. Then, a 4" length of TYGON™ (Trademark of the Saint-Gobain Corporation) tubing (outside diameter (OD): 3/8 inch, inside diameter (ID): 1/4 inch, and a wall thickness of 1/16 inch) was attached to the outer part of the fitting.

A plastic clamp was placed on the middle of the tubing and squeezed to close it off. Five grams of granular composite (or other test material) was added into the container so that the granular composite is distributed homogeneously in the bottom of the container. The vial was placed in the large container, and a certain amount and type of malodor was added to the vial. Unless otherwise noted, a volume of 600 microliters of 0.9% saline solution containing 1200ppm ammonia (based on the weight of solution) or 1200ppm TMA was used as control malodor solution. The container was immediately sealed with a lid incorporating an aluminum fitting. The end of the TYGON tubing was connected to the aluminum fitting on the top of the lid. Both tips of the appropriate Draeger short-term gas detection tube were broken off using a tube cutter. The end was inserted into the Tygon tubing so the flow indicator arrow pointed away from the testing apparatus. After an appropriate amount of time, the outer end of the gas detection tube was inserted into the hand pump, and the clamp on the tubing was released. The hand pump was completely depressed (at which point, the number on the counter at the top of the pump increased by one) and then released, and air was allowed to flow through the tube. One hundred cubic centimeters of air flow through the tube with each cycle. The cycle is finished when the indicator on the top of the pump turns white. The material in the tube will change color to indicate gas detection. The ppm level from the gradients on the side of the tube was read and recorded. The ammonia tubes (part number CH20507, 5-70ppm range, color change from yellow to blue) and TEA tubes (detection for TMA; part number 6718401, 5-60ppm range, color change from yellow to blue) measured levels in ppm gradations. Hand pump depression and malodor level readings were repeated four more times, recorded after each cycle (stroke), and resulted in a total of 500cm³ of air pumped through the gas detection tube.

In- Line Filter Testing Procedures An aluminum fitting was placed on the cap of a 1 -gallon plastic container (large container) with a hole cut in center of the lid, followed by securely finger-tightening the fitting. Then, a 4" length of Tygon™ tubing (outside diameter (OD): 3/8 inch, inside diameter (ID): 1/4 inch, and a wall thickness of 1/16 inch) (Trademark of the Saint-Gobain Corporation) was attached to the outer part of the fitting. A plastic clamp was placed on the middle of the tubing and squeezed to close it off. The vial was placed in the large container, and a certain amount and type of malodor was added to the vial. Unless otherwise noted, a volume of 5.4mL of 0.9% saline solution containing 1200ppm ammonia (based on the weight of solution) or 1200ppm TMA was used as control malodor solution. The container was immediately sealed with a lid incorporating an aluminum fitting. Filter material was added to an inline filter so that it is level with the top of the metal ring. The weight was recorded. Dimensions of inline filter components were as follows:

Outer fitting: OD = 1 ¹Z₂"; large ID = 1 VA" ; small ID = ³A"; height = 5/8" Inner fitting: OD = 1 Vi"; OD of threads = 1 ¹A"; ID = ³A"; height = 5/8" Connectors: OD = just under 1 ¹A" ; ID tube = just under and just over ¹A" ; height =

7/8"

Metal ring: OD = 7/8" ; ID = ³A" ; height VA" O-ring: OD = 1 ¹A"; ID = 13/16" Screens: OD = 1 VA" The entire filter was assembled and was then attached to the end of the Tygon tubing on the top of the lid. Both tips of the appropriate Draeger short-term gas detection tube were broken off using a tube cutter. The end was inserted into the Tygon tubing so the flow indicator arrow pointed away from the testing apparatus. After an appropriate amount of time (typically 3 hours, unless otherwise stated), the outer end of the gas detection tube was inserted into the hand pump, and the clamp on the tubing was released. The hand pump was completely depressed (at which point, the number on the counter at the top of the pump increased by one) and then released, and air was allowed to flow through the tube. One hundred cubic centimeters of air flow through the tube with each cycle. The cycle is finished when the indicator on the top of the pump turns white. The material in the tube will change color to indicate gas detection. The ppm level from the gradients on the side of the tube was read and recorded. The ammonia tubes (part number CH20507, 5-70ppm range, color change from yellow to blue) and TEA tubes (for TMA detection; part number 6718401, 5-60ppm range, color change from yellow to blue) measured levels in ppm gradations. Hand pump depression and malodor level readings were repeated four more times, recorded after each cycle (stroke), and resulted in a total of 500cm³ of air pumped through the gas detection tube.

Example 1: Extrusion of Granular Composite Samples with KITCHENAID™ Mixer The fine-sized SAP materials ("fines") and the regular SAP were used to prepare different dry blend materials as shown in Table 5. The amount of DLP was kept at 2.5wt.% and both fines and regular SAP at 25wt.%. The composite blends (see Table 5) were extruded using a KitchenAid stand mixer with the paddle attachment. The motor was engaged slowly, and 20Og (2 times the weight of the dry components) of deionized water was slowly added to the mixer. Dough of an agglomerated, peanut-sized material was formed by mixing the water and dry components. Once thoroughly mixed, the motor was turned off, and the wet mixture was extruded through the food grinder attachment on the mixer using the disc with larger holes (diameter of about 6mm). The resulting material was dried in an oven at 105⁰C for 1 hour.

Table 5: Granular Composite Samples Prepared using KITCHENAID T¹"M¹ Type Extruder

The mixture using regular SAP was more segregated and harder to extrude than the mixture containing the fines. The recipe using the SAP fines was homogeneous and easy to work with. The clumping absorption test for granular composite samples from the KitchenAid extrusion experiment was conducted using synthetic urine solution and the results are shown in Table 6.

Table 6: Clumping Absorption Test for Granular Composite Samples

The results shown in Table 6 indicate that a sodium bentonite clay composite comprising a DLP with a very high absorbency function is possible. The resulting composites from the KitchenAid experiment also show that the composite granules have good clumping formation with synthetic urine solution.

Example 2: Extrusion of Granular Composite Samples using Nica Low-Pressure Basket Extruder Two samples were prepared while the amount of Pergopak M was varied (0 or 5wt.%), based on the total dry blend material. Pergopak M was added to the blend material (2.0kg) prior to wetting with water (2.0kg). In both cases, DLP was kept at 2.5wt.%.

Table 7: Extrusion of Granular Composite Samples (Type A) using Nica Low-Pressure Basket Extruder

Example 3: Centrifuged Retention Capacity (CRC) and Absorption Under Load (AUL) of the Composite Granules

The granular composite samples (type A) obtained from Example 2 were measured for their absorbencies. CRC measurements were conducted in a solution of 0.9% saline and deionized water, and the results are shown in Table 8. The data there represent an average of duplicate measurement. AUL was measured using 0.9% NaCl solution.

Table 8: Absorbency Results for Composite Granules

Despite the small fraction of the SAP in the composite granules (i.e., 25 wt %), the composite granules show a very high absorbency. The results in Table 8 show the effects of the salinity on the absorbency, for example, water vs. saline. The composite granules seem to be less negatively affected by the presence of the pressure. The presence of Pergopak M at 5wt.%, which is a non-swelling material, seems to reduce absorbencies for the Pergopak M containing sample (dilution effect). The free swelling of the pure sodium bentonite is expected to be approximately 7.5 - 8.0g/g in water. No control CRC and AUL data for the pure bentonite are available. However, the corresponding CRC and AUL values in saline for the bentonite are expected to be much smaller than the free-swell capacity of the bentonite in water. The absorbency data of both composite granules suggest that the super absorbency in the composite granules is intact. Example 4: Clumping Absorption Testing and Effects of PERGOPAK™ M

In Table 9, the results for clumping absorption tests of non-Pergopak M and Pergopak M containing composite granule samples (type A) are shown. Numbers are the averages from five independent experiments, and those in parentheses are the standard deviation from five independent experiments. Clumps from the composite granules (type A) are rather cylindrical as the dimension numbers in Table 9 indicate. The sample containing Pergopak M absorbed more quickly since the clump was much shallower. The Pergopak M containing composite granules seem to better utilize the granules than the non-Pergopak M sample, as shown in lower clump weight.

Table 9: Effects of Pergopak M on Clumping Absorbency

Example 5: Effects of Pergopak M on Speed of Absorption

The findings in Table 9 seem to indicate a faster absorption due to a better porosity on the surface. The findings also indicate that the penetration of the liquid front seems longer for the non-Pergopak M than the Pergopak M containing sample (type A) from Example 2 (see Table 7). In order to check this effect, we conducted an experiment as follows. Approximately 7OmL of composite granules was added to two 8OmL beakers approximately 80mm deep (one with and one without Pergopak M), and 2mL synthetic urine was added to each beaker. After one hour, the clump was removed, weighed, and measured. The results are summarized in Table 10.

Table 10: Effects of Pergopak M on Speed of Absorption

Based on penetration of the liquid front (depth), the liquid front more freely penetrates the non-Pergopak M containing granule sample than the Pergopak M-containing sample.

Example 6: Extrusion Experiments and Effects of DLP

In the experiments shown in Table 11, the amount of DLP was varied from 0 to 5wt.%. In all cases, Pergopak M was kept at 5wt.% based on the total dry blend material. In Table 12, the results for clumping tests of different composite granule (type A) samples are shown. Numbers are the averages from five independent experiments.

Table 11: Extrusion Experiments using Nica Low-Pressure Basket Extruder at Varying Amounts of DLP

Table 12: Clumping Absorption Testing with Synthetic Urine Added to the Composite Granules

In the experiments shown in Table 12, Scoop Away TM cat litter (Clorox Company) is used as a control. The DLP containing granular composite samples in Table 12, for example, Blend 2.5 and Blend 5 outperform the Scoop Away sample with regard to the clump absorbency. Scoop Away cat litter clumps are found hemisphere-shaped, deeper at the center, and becoming shallower at the edges. The numbers measured are at both the center and the edge since they are not cylindrical.

Example 7: Effects of Varying Amounts of Liquids

In another experiments, the granule samples having different amounts of DLP (shown in Table 11) were added with varying amounts of synthetic urine ranging from 1 to 5mL for clumping absorbency testing. The results are summarized in Table 13.

Table 13: Results for Clumping Absorbency at Varying Amounts of Synthetic Urine

The trend in Figure 1 shows a good correlation (R square) between clump weight and added synthetic urine amount. The results in Table 13 and Figure 1 show that with increasing amounts of DLP, the composite granules result in a lower clump weight, and therefore, a granular composite with higher clumping absorbency.

Example 8: Odor Control Efficacy

The odor control efficacy of the composite samples shown in Table 11 was checked at a concentration of TMA of 800 ppm (based on the weight of the synthetic urine solution). The odor control efficacy was then compared with that of Scoop Away ("Fresh Scent, Maximum Odor Control"), the commercial cat litter product of the Clorox Company.

The results for odor control efficacy of the different composite samples (type A) are summarized in Table 14.

Table 14: Results for Odor Control Composite Granules (Type A) at TMA level of 800ppm

The overall results indicate malodor control potential of the granular composites in many different application areas, including uses in air care, for example, in air filtration areas. For cat litter applications, an odor control function is important, and the granular composite of the present invention shows an odor control efficacy that outperforms Scoop Away.

Example 9: Experiments using Nica Low-Pressure Basket Extruder and Effects of Porous Polymer Adsorbent and Methocel™

Porous polymer adsorbent, Dow Optipore™ V503 (hereafter, V503), from The Dow Chemical Company and Methocel™ A4M is used in powder form as a special additive for the composite granule at a level of 5 wt.% and 2.5 wt.% respectively. The extrusion experiments are shown in Table 15. Table 15: Extrusion of Composite (type A) Samples using Nica Low-Pressure Basket Extruder

a) Used as a ground form <250 microns, b) Used as powder as obtained

The polymer adsorbent V503 and Methocel containing composite sample gave slightly less sticky extruded strands than the granular composite sample. The addition of porous polymer adsorbent V503 and Methocel showed no changes in extrusion processibility. The clump weights of the polymer adsorbent and Methocel containing samples are comparable to the granular composite sample.

Example 10: GC Experiments for TMA

The results from measuring the interaction of TMA with composite samples (granular composite type A; see Table 15) are summarized below in Table 16. Numbers in parentheses are the percent TMA reduction relative to the control (TMA vial). If the GC experiments were done with an amount of lμL of 2.1% TMA/water solution per vial at the equilibration time overnight, the TMA result showed that the average peak area from the duplication experiment in control injections (TMA present, no granular composites) was 187876. TMA was not detected in blank vials (no TMA, with adsorbent) and the all three sample vials (TMA with composite particles) irrespective of the types of additives in Table 15. The GC experiments were repeated with an increased amount of TMA/water solution. The procedure was the same as the last set of measurements except that the amount of 2. l%TMA/water solution per vial was increased from lμL to lOμL. Also, the equilibration time was 3-4 hours instead of overnight. Table 16: Results for GC Experiments for TMA

a) Non-detectable

The results in Table 16 show that all granular composite samples significantly reduce the TMA concentration in the headspace. For example, the headspace malodor TMA concentration of the solution control is reduced by the presence of granular composite samples by 98 to 100 percent. The efficacy of the Methocel A4M containing sample seems slightly better than the composite samples with polymer adsorbent V503 or the granular composite sample.

Example 11: GC Experiments for DMDS

The peak areas detected for DMDS in a study of the interaction of the composite samples (see Table 15) are given below in Table 17. Numbers in parentheses are the percent DMDS reduction relative to the control (DMDS vial). Numbers are average values from the duplication experiment.

Table 17: Results for GC Experiments for DMDS

a) One measurement

No adsorption was detected for the granular composite and Methocel A4M sample.

However, the headspace malodor DMDS concentration of the solution control is significantly reduced by the presence of granular composite comprising polymer adsorbent V503, for example, by 93 percent.

Example 12: GC Experiments for Formaldehyde

The peak areas detected for formaldehyde in the presence of the composite (type A) samples (see Table 15) are given below in Table 18. The numbers were obtained from one measurement. Table 18: Results for GC Experiments for Formaldehyde

a) Non-detectable

The data show that all three composite samples reduced the formaldehyde concentration in the headspace, irrespective of the formaldehyde concentrations. Granular composite outperformed the other composites containing Methocel A4M or polymer adsorbent V503 when a 3.9% formaldehyde solution was used. Granular composite appeared to be slightly better than the other composites containing Methocel A4M or polymer adsorbent V503 when a 37% solution was used.

Example 13: GC Experiments for Styrene Monomer

The results from measuring the interaction of styrene monomer with composite samples (see Table 15) are summarized below in Table 19. The results were obtained from a duplication experiment. Numbers in parentheses are the percent styrene reduction relative to the control (styrene monomer).

Table 19: GC Experiments for Styrene Monomer

All compositions further significantly reduced the styrene monomer concentration in the headspace. For example, the headspace styrene monomer concentration of the control is reduced by the presence of granular composite samples by 44 to 99.5 percent. The efficacy of the polymer adsorbent V503 composite significantly enhances the performance over the granular composite or Methocel A4M sample. Example 14: GC Experiments for DMP

The results from measuring the interaction of DMP and composite samples (see Table 15) are summarized below in Table 20. The results were obtained from a duplication experiment. Numbers in parentheses are the percent DMP reduction relative to the control (DMP).

Table 20: GC Experiments for Dimethylphthalate (DMP)

a) The result was obtained from a triple experiment.

All composite samples significantly reduce the DMP concentration in the headspace.

For example, the headspace DMP concentration of the control is reduced by the presence of granular composite samples by 50 to 67 percent. The efficacy of the polymer adsorbent V503 and granular composite sample show a slightly better performance over the composite samples with Methocel.

Example 15: Experiments Using Nica Low-Pressure Basket Extruder and Effects of Citric

Acid and Glass Beads

Citric acid (CAS# 77-92-9, ACS reagent, Aldrich) was used in powder form as a special additive for the composite granule at a level of 25 wt.%. Glass beads (CAS#: 65997- 17-3,

P0040; size: 0.1 mm or finer) from Potter Industries (Westlake, OH 44145) were used in powder form as a special additive for the composite granule at a level of 5 wt.% and 10 wt.% respectively. The extrusion experiments are shown in Table 21.

Table 21: Extrusion of Composite Samples Using Nica Low-Pressure Basket Extruder

The glass beads containing composite samples gave normal extruded strands, and the citric acid containing composite samples gave slightly stickier extruded strands than the granular composite sample. The addition of citric acid and glass beads showed no changes in extrusion processibility. The dried composite materials were ground and then sifted using a 150- and 1200-microns sieve prior to use (see Table 22).

Example 16: Large Container Head Space Gas Detection Experiment for Ammonia Concentrations (ppm) and Effects of Citric Acid and Glass Beads

Table 22 below gives the concentrations detected for ammonia in the head space of the large container in a study of the interaction of the composite samples (see Table 21). The numbers in Table 22 are the parts per million (ppm). A 0.9% saline solution (600 microliters) with 1200ppm Ammonia was used as control malodor solution.

Table 22: Results for Large Container Head Space Gas Detection Experiment for Ammonia Concentrations (ppm)

a) Particle size fraction is between 150 microns and 1200 microns. The data show that the control malodor solution increased the ammonia concentration in the headspace with increasing strokes, irrespective of the time. The ammonia gas concentration seemed to reach a peak around 3 to 6 hours. The control malodor solution data also indicated that there was a slight natural decay of the ammonia concentration in the head space that seemed to be based on adsorption of the ammonia gas molecules on the wall of the large container. This was seen overnight, typically a time period of 16 hours. All granular composite samples reduced the ammonia concentration in the headspace, irrespective of the time. With increasing time, a higher efficacy of the malodor control was found. Both glass beads containing granular composite appeared to be slightly better than the granular composite. The efficacy of the 10% glass beads composite seemed to enhance the performance over the granular composite sample and 5% glass bead composite sample. The citric acid containing granular composite significantly reduced the ammonia concentration further in the headspace. The efficacy of the citric acid containing granular composite seemed to outperform the performance of the granular composite or glass bead containing samples.

Example 17: Experiments using Fuji Paudal High-Pressure Extruder and Effects of Potassium Hydroxide

Potassium hydroxide flakes (CAS# 1310-58-3, technical grade, JT Baker) were used in fine flake form as a special additive for the composite granule at a level of 10 wt.%. The wetted material was extruded using a Fuji Paudal high pressure extruder (Type: EXD-60, Fuji Paudal Company Ltd., Osaka, Japan). The extrusion experiments are shown in Table 23.

Table 23: Extrusion of Composite Samples Using Fuji Paudal High-Pressure Extruder

The potassium hydroxide containing samples gave normal extruded strands. Extrusion time was quick, about 5 minutes, and the extrudate was dried normally. The addition of potassium hydroxide showed no changes in extrusion processibility. The dried composite materials were ground and then sifted using a 150- and 1200-microns sieve prior to use (see Table 24). Example 18: Large Container Head Space Gas Detection Experiment for Ammonia Concentrations (ppm) and Effects of Potassium Hydroxide and Citric Acid

The different granular composite samples, including an ammonia malodor solution, granular composite, potassium hydroxide containing granular composite samples (with or without SAP), and citric acid containing granular composite sample (see Table 21) were tested for their ammonia malodor efficacies at different times, for example, ranging from 1 hour to 16 hours (overnight). A 0.9% saline solution (600 microliters) with 1200ppm Ammonia was used as control malodor solution. The results are shown in Table 24.

Table 24: Results for Large Container Head Space Gas Detection Experiment for Ammonia Concentrations (ppm)

a) Particle size fraction is between 150 microns and 1200 microns. b) Sample taken from Table 21. Independent measurement.

The data in Table 24 show that the control malodor solution increased the ammonia concentration in the headspace with increasing strokes, irrespective of the time. The ammonia gas concentration seemed to reach a peak around 3 to 6 hours. The control malodor solution data also indicated that there is a slight natural decay of the ammonia concentration in the head space due to the adsorption of the ammonia gas molecules on the wall of the large container. This was seen overnight, typically a time period of 16 hours. The granular composite sample reduced the ammonia concentration in the headspace, irrespective of the time. Again, with increasing time, a higher efficacy of the malodor control was found. The citric acid containing granular composite further significantly reduced the ammonia concentration in the headspace. The efficacy of the citric acid containing granular composite seemed to outperform the granular composite, which is in agreement with the results shown in Table 22. Both potassium hydroxide containing granular composites, irrespective of the presence of the SAP, appeared to be less effective for the basic malodor (like the ammonia used in the testing) than the granular composite and the citric acid containing granular composite.

Example 19: Surface Coating of Granular Composite Using Orange Oil and Effects on Odor Control Efficacy

An orange oil (CAS#:8008-57-9, cold-pressed, California, Aldrich) was used as a special additive for the composite granules at a level of 2 wt.% (based on the dry weight of the granular composite). The dry granular composite material (lOOgrams) having a particle size fraction between 150 microns and 1200 microns was put into a 50OmL PE bottle, a few droplets of orange oil were added onto the walls, and the bottle was closed and hand- shaken for 3-5 minutes until all droplets had visibly disappeared. The procedure was repeated until the all the orange oil was used. The coating procedure resulted in free-flowing, non- coagulated granules, and is termed hereafter the fragranced granular composite.

Example 20: Large Container Head Space Gas Detection Experiment for Ammonia

Concentrations (ppm) and Effects of Orange Oil Fragrance

The orange oil-treated, fragranced granular composite sample was tested for its ammonia malodor efficacy at two different times, for example, 1 hour and 3 hours. A 0.9% saline solution (600 microliters) with 1200ppm Ammonia was used as control malodor solution. The results are shown in Table 25, and compared with those from the granular composite run under the same conditions.

Table 25: Results for Large Container Head Space Gas Detection Experiment for Ammonia Concentrations (ppm) and Effects of Orange Oil Fragrance

a) Particle size fraction is between 150 microns and 1200 microns.

The data show that the control malodor solution increased the ammonia concentration in the headspace with increasing strokes. A slightly lower ammonia concentration was detected for 3 hours than expected for the control malodor solution. However, the fragranced granular composite sample reduced the ammonia concentration in the headspace, irrespective of the time. Again, with increasing time, a higher efficacy of the malodor control was found.

Example 21: Large Container Head Space Gas Detection Experiment for TMA Concentrations (ppm) and Effects of Orange Oil Fragrance

The orange oil-treated, fragranced granular composite sample was tested for its TMA malodor efficacy at two different times, for example, 1 hour and 3 hours. The results, shown in Table 26, are compared with those from the granular composite run under the same conditions. A 0.9% saline solution (600 microliters) with 1200ppm TMA was used as control malodor solution.

Table 26: Results for Large Container Head Space Gas Detection Experiment for TMA Concentrations (ppm)

a) Particle size fraction is between 150 microns and 1200 microns.

The data show that the control malodor solution increased the TMA concentration in the headspace, irrespective of the time. The TMA concentration increased to a higher level of TMA after 3 hours. The fragranced granular composite sample reduced the TMA concentration in the headspace with increasing strokes, irrespective of the time. With increasing time, a higher efficacy of the TMA malodor control was found for the fragranced granular composite.

Example 22: Fragranced Odor Control Granule and Comparison with Cat Litter

The odor control efficacy of the composite sample and fragranced composite sample was checked at a TMA concentration of 1200 ppm (based on the weight of the synthetic urine solution). The odor control efficacy was then compared with that of Scoop Away™¹ ("Fresh Scent, Maximum Odor Control"), the commercial cat litter product of the Clorox Company, and the results are shown in Table 27.

Table 27: Results for Granular Composite and Fragranced Granular Composite at TMA Level of 1200ppm

a) Used as obtained. b) Particle size fraction is between 150 microns and 1200 microns.

The results in Table 27 indicate that the fragranced granular composites show a synergistic effect with regard to malodor control. The results also indicate the potential malodor control in different air care application areas such as air fresheners where a controlled release of fragrance is necessary. For cat litter applications, both granular composite and the fragranced granular composite of the present invention show an odor control efficacy that significantly outperforms Scoop Away.

Example 23: Large Container Head Space Gas Detection Experiment for Ammonia Concentrations (ppm) and Effects of Baking Soda

The concentrations detected for ammonia in the head space of the large container in a study of the interaction of the composite sample and ARM&HAMMER™ baking soda which is a commercial deodorizer product of Church&Dwight Co., Inc. are given below in Table 28.

The numbers in Table 28 are in parts per million (ppm). A 0.9% saline solution (600 microliters) with 1200ppm Ammonia was used as control malodor solution. Table 28: Results for Large Container Head Space Gas Detection Experiment for Ammonia Concentrations (ppm)

a) Used as obtained. b) Particle size fraction is between 150 microns and 1200 microns.

The data in Table 28 show that the control malodor solution increased the ammonia concentration in the headspace with increasing strokes, irrespective of the time. The control malodor solution data over a period of 3 days seemed to show a strong natural decay of the ammonia concentration in the head space due to the adsorption of the ammonia gas molecules on the wall of the large container. The fine baking soda powder sample did not reduce the ammonia concentration in the headspace, irrespective of the time. The ammonia concentration in the headspace was found to be almost identical to that of the malodor control solution. The granular composite sample reduced the ammonia concentration in the headspace, irrespective of the time. Again, with increasing time, a higher efficacy of the malodor control was found.

Example 24: Experiments Using Nica Low-Pressure Basket Extruder and Effects of Activated Carbon PAC200

Activated carbon PAC200 (CAS#: 7440-44-0; Norit Americas Inc., TX 75670, USA) was used in fine powder form as a special additive for the composite granules at a level of 20 wt. %. The activated carbon powder was used as obtained. The extrusion experiments are shown in Table 29.

Table 29: Extrusion of Composite Samples Using Nica Low-Pressure Basket Extruder

The activated carbon-containing composite samples gave normal extruded strands. The addition of citric acid and glass beads showed no changes in extrusion processibility. The dried composite materials were ground and then sifted using a 150- and 1200-microns sieve prior to use (see Table 30).

Example 25: Large Container Head Space Gas Detection Experiment for Ammonia Concentrations (ppm) and Effects of Activated Carbon

The odor control efficacy of the activated carbon-containing composite sample was checked at an ammonia concentration of 1200 ppm at several different times, ranging from 1 hour to 5 days. The odor control efficacy was also compared with that of pure activated carbon powder PAC200, and the results are shown in Table 30. The data there represent an average of duplicate measurement. An amount of 3.6mL of 0.9% saline solution having 1200ppm ammonia concentration was used as control malodor solution.

Table 30: Results for Large Container Head Space Gas Detection Experiment for Ammonia Concentrations (ppm)

a) Exceeds slightly the Draeger tube range of Oppm to 70ppm. b) Particle size fraction is between 150 microns and 1200 microns. c) Used as obtained. Very fine powder, less than 45 microns (min. 50%), less than 75 microns (88%) and less than 150 microns (96%); Iodine number (mg/g) = 900 min.

The data indicate that the control malodor solution increased the ammonia concentration in the headspace with increasing strokes, irrespective of the time. The ammonia gas concentration showed a high ammonia concentration at times of 3 hours to 3 days. And the control malodor solution data at prolonged time period (such as 5 days) seemed to show a substantial natural decay of the ammonia concentration due to the adsorption of the ammonia gas molecules on the wall of the large container. The granular composite sample reduced the ammonia concentration in the headspace. With increasing time, a higher efficacy of the malodor control was found, and no ammonia was detected at times, for example, of 3 and 5 days.

The pure activated carbon PAC200 sample significantly reduced the ammonia concentration in the headspace in the first few hours, for example, 1 and 3 hours. The efficacy of the pure activated carbon power sample PAC 200 seemed to be equal to or slightly outperforming the performance of the granular composite up to 3 hours based on its higher surface areas as compared to the granular composite. However, the efficacy of the pure activated carbon power sample PAC 200 seemed to be deteriorating with time, and becoming less effective than that of the granular composite at 3 days or after. It is interesting to note the strong increase of the ammonia concentration at 3 days, which then becomes somewhat smaller at 5 days, in part due to the natural decay effect, but still higher than that of the granular composite. It is very interesting to note that the odor control efficacy of the activated carbon- containing composite sample (20wt% activated carbon based on the dry weight of the granular composite sample) was found to be intermediate between the two samples (pure activated carbon powder PAC200 and the granular composite) in the first few hours. The 20% PAC 200 granular composite sample seems to not be as effective as the granular composite but it still seems to outperform the pure activated carbon powder PAC sample at 3 days or later.

Example 26: Inline Filter Testing for Various Activated Carbon and Granular Composite Samples

The odor control efficacies of various types of activated carbon samples and zeolite sample (Abscents 3000, from the UOP Company, particle diameter of about 3 microns; CAS#: 76774-74-8) were checked at an ammonia concentration of 1200 ppm by inline filter testing. The test activated carbon samples include pure activated carbon powder PAC200, Norit RBAAl extruded pellets and Norit RO 0.8 extruded pellets. An amount of 5.4mL of 0.9% saline solution with a 1200ppm ammonia concentration was used as control malodor solution. The test time was kept at 3 hours. The results are shown in Table 31. The weight of each material used in the inline filter testing is also shown in Table 31.

Table 31 : Results for Inline Filter Testing for Ammonia Concentrations (ppm)

a) Particle size fraction is between 150 microns and 1200 microns. b) <150 microns c) Very fine powder, less than 45 microns (min. 50%), less than 75 microns (88%) and less than 150 microns (96%); Iodine number (mg/g) = 900 min. d) Extruded pellets; apparent density = 0.53g/cm3 e) Extruded pellets; apparent density = 0.40g/cm3; BET = 1300m2/g f) Very fine powder of particle diameter of about 3 microns

The various activated carbon samples show relatively high ammonia concentration after passing through the inline filter, irrespective of the form of the activated carbon. The efficacy of the pure zeolite, Abscents 3000 seems to be comparable with or slightly outperform the performance of the citric acid-containing granular composite with a relatively coarse particle sizes, for example, between 150 microns and 1200microns. However, the efficacy of the fine sized citric acid-containing granular composite seemed to become more effective so that no ammonia could be detected. Example 27: Inline Filter Testing for Various Pre-filters Containing Activated Carbon

The odor control efficacy of an activated carbon-containing pre-filter for air cleaners was checked at an ammonia concentration of 1200 ppm by inline filter testing. The test sample includes the Hamilton Beach TrueAir Air Cleaner Pre-filter. The activated carbon- containing pre-filter was cut into a 5/8" circle and placed into the inline filter. An amount of 600 microliters of 0.9% saline solution with a 1200ppm ammonia concentration was used as control malodor solution. The test time was kept at 3 hours. The results are shown in Table 32.

Table 32: Results for Inline Filter Head Space Gas Detection Experiment for Ammonia Concentrations (ppm) Detected in Head Space

a) <150 microns b) Activated carbon-containing air cleaner replacement pre-filter, purchased from Lowes retail market.

The activated carbon-containing pre-filter, the Hamilton Beach True Air Pre-filter, shows relatively high ammonia concentration when used as filter media in the inline filter. The efficacy of the granular composite fines (particle sizes smaller than 150 microns) is shown in Table 32. The fine sized granular composite seems to be an effective filter medium. It is understood that the present invention is not limited to the embodiments specifically disclosed and exemplified herein. Various modifications of the invention will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the appended claims.

Moreover, each recited range includes all combinations and subcombinations of ranges, as well as specific numerals contained therein. Additionally, the disclosures of each patent, patent application, and publication cited or described in this document are hereby incorporated herein by reference, in their entireties.

Claims

Claims:

1. A granular composite comprising a) an inorganic particulate, b) a redispersible latex powder, and c) one or more of a superabsorbent polymer, a porosity-enhancing agent, a water-soluble polymer, an odor control agent, or an oil-absorbing agent.

2. The composite of claim 1, wherein the inorganic particulate is clay.

3. The composite of any one of claims 1 to 2, wherein the inorganic particulate is sodium bentonite clay.

4. The composite of any one of claims 1 to 3, wherein the composite comprises at least lwt.% of inorganic particulates.

5. The composite of any one of claims 1 to 4, wherein the composite comprises at least 0.1 wt. % of redispersible latex powder.

6. The composite of any one of claims 1 to 5, wherein the composite comprises at least 0. lwt.% of a superabsorbent polymer.

7. A granular composite comprising a) a clay, and b) a redispersible latex powder, wherein the composite comprises more than 15wt.% of clay based on the combined weight of the clay and the redispersible latex powder.

8. The composite of any one of claims 1 to 7, further comprising an alcohol, a fragrance agent, a surfactant, a pigment, a colorant, a moisture -reactive indicator, a pH indicator or a mixture thereof.

9. The composite of claim 1 comprising an odor control agent, wherein the odor control agent is one or more of an activated; a cyclodextrin; a porous polymer adsorbent; an ion exchange polymer; sodium bicarbonate; borax; a peroxide such as sodium, potassium or ammonium percarbonate, peroxide, peroxodisulfate and permanganate; a biocide; a plant extract such as extract and/or dry powder of green tea leaves, olive leaves, yucca, aloe, and Quillaja; citric acid; chelating agents; natural and synthetic zeolites; perfumes; various metals and metal compounds; metallic and ionic silver in various forms; chitosan, or a mixture thereof.

10. A granular composite comprising: a) 1 to 99wt.% of clay; b) 0.1 to 25.0wt.% of redispersible latex powder; c) 0.1 - 99wt.% superabsorbent polymer (SAP); d) 0.1 - 25wt.% water-soluble polymer; e) 0.01 - 25wt.% porosity-enhancing agent; f) 0.01 - 25wt.% odor control agent; and g) 0.01 - 25wt.% water.

11. A process of making any one of the composite of claims 1 to 10 comprising dry blending clay, redispersible latex powder, and other ingredients of the composite to form a mixture; wetting the mixture with water or aqueous solution; extruding the wet mixture to form the granular composite; drying the extruded material; sizing and sieving to form the composite; remoisturizing the composite; and dedusting the composite.

12. An article comprising a granular composite of any one of claim 1 to 10.