WO2002040149A2

WO2002040149A2 - Acid contacted enhanced adsorbent particle, binder and oxide adsorbent and/or oxide catalyst system, and method of making and using therefor

Info

Publication number: WO2002040149A2
Application number: PCT/US2001/045004
Authority: WO
Inventors: Mark L. Moskovitz; Bryan E. Kepner; Eric A. Mintz
Original assignee: Apyron Technologies, Inc.
Priority date: 2000-11-17
Filing date: 2001-11-15
Publication date: 2002-05-23
Also published as: AU2002236531A1; WO2002040149A3

Abstract

This invention relates to a process for producing an enhanced absorbent particle comprising contacting a non-amorphous, non-ceramic, crystalline, porous, calcined, aluminum oxide particle that was produced by calcining at a particle temperature of from 300 °C to 700 °C, with an acid for a sufficient time to increase the adsorbent properties of the particle. A process for producing an enhanced adsorbent particle comprising contacting a non-ceramic, porous, oxide adsorbent particle with an acid for a sufficient time to increase the adsorbent properties of the particle is also disclosed. Particles made by the process of the instant invention and particle uses, such as remediation of waste streams, are also provided. The invention also relates to a method for producing an adsorbent and/or catalyst and binder system. The invention also relates to particles made by the process, binders, and methods for remediating contaminants in a stream. The invention also relates to an anchored adsorbent and/or catalyst and binder system.

Description

ACID CONTACTED ENHANCED ADSORBENT PARTICLE, BINDER AND

OXIDE ADSORBENT AND/OR OXIDE CATALYST SYSTEM, AND METHOD

OF MAKING AND USING THEREFOR

BACKGROUND OF THE INVENTION

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application serial no. 09/715,542, filed on November 17, 2000, which is incorporated by reference in its entirety.

FIELD OF THE INVENTION

This invention relates generally to enhanced adsorbent particles, particularly particles that have been adsorbent enhanced by contacting with acid. This invention also relates generally to an adsorbent and/or catalyst particle that has improved adsorbent properties and/or improved or newly existing catalytic properties by the use of the particle in combination with a particular binder to produce a particle binder system. The binder can either cross-link to the particle, cross-link to itself and envelope the particle or both This invention also relates to a binder/adsorbent and/or catalyst system that can be used as an anchored catalyst system and/or chromatography support. BACKGROUND ART

Oxides of metals and certain non-metals are known to be useful for removing constituents from a gas or liquid stream by adsorbent mechanisms. For example, the use of activated alumina is considered to be an economical method for treating water for the removal of a variety of pollutants, gasses, and some liquids. Its highly porous structure allows for preferential adsorptive capacity for moisture and contaminants contained in gasses and some liquids. It is useful as a desiccant for gasses and vapors in the petroleum industry, and has also been used as a catalyst or catalyst-carrier, in chromatography and in water purification. Removal of contaminants such as phosphates by activated alumina are known in the art. See, for example, Yee, W., "Selective Removal of Mixed Phosphates by Activated Alumina,'¹ J.Amer.Waterworks Assoc, Vol. 58, pp. 239-247 (1966).

U.S. Patent No. 4,795,735 to Liu et al. discloses an activated carbon/alumina composite and a process for producing the composite. The composite is prepared by blending powders of each of the activated carbon and activated alumina constituents. After the blend is thoroughly mixed, an aqueous solution is added to permit the activated alumina to rehydratably bond to the carbon particles. The amount of water added does not exceed that which prevents the mix from being extruded or agglomerated. After the water is added, the mix is subjected to a shaping or a forming process using extrusion, agglomeration, or pelletization to form a green body. The green body is then heated to a temperature of 25- 100° C or higher. The composite may be strengthened by peptizing by adding nitric acid to the mixture. It is disclosed that the alumina can serve as the binder as well as the absorbent. This patent does not use a calcined durnina. Liu et al. discloses an amorphous alumina trihydrate powder, such as CP2 obtained from Alcoa and an amorphous -dumina trihydrate powder such as CP-1 or CP-7, which are recited in U.S. Patent No. 4,579,839, incorporated by reference in Liu et al. Liu et al. 's use of the term active refers to the surface water being dried and does not refer to a calcined particle. Liu et al. uses acid to strengthen the particle and not to enhance its adsorbent properties. Liu et al. uses an -ilumina precursor, which is an absorbent and not an adsorbent.

U.S. Patent No. 3,360,134 to Pullen discloses a composition having adsorption and catalytic properties. Example 2 discloses an alumina hydrate formed by partially dehydrating alpha-alumina trihydrate in a rotary dryer by counter-current flow with a heated gas and an inlet temperature of about 1200 °F and an outlet temperature of about 300 °F. The resulting product was washed with 5% sulfuric acid, rinsed with water and dried to about 2% free water content. Solid sucrose was mixed with the hydrate and the mixture heated. Example 4 discloses that the procedure of Example 2 was repeated except that calcined alumina was used. The product was unsuitable when calcined alumina was used. Thus, the acid washed product of Example 2 was not a calcined -ilumina.

U.S. Patent No. 4,051,072 to Bedford et al. discloses a ceramic -dumina that can be treated with very dilute acid to neutralize the free alkaline metal, principally Na₂θ, to enable impregnation with catalytic material to a controlled depth of from at least 90 to about 250 microns. This patent does not use a crystallized aluminum oxide that has been calcined in accordance with the instant invention. This patent calcines the particle at a temperature of from about 1700°F to about 1860°F (927 °C to 1016°C) to form a ceramic material, specifically what is referred to herein as an alpha -dumina.

U.S. Patent No. 5,242,879 to Abe et al. discloses that activated carbon materials, which have been subjected to carbonization and activation treatments, and then further subjected to an acid treatment and a heat treatment, have a high catalytic activity and are suitable as catalysts for the decomposition of hydro gen peroxide, hydrazines or other water pollutants such as organic acids, quaternary ammonium- salts, and sulfur-containing compounds. Acid is used to remove impurities and not to enhance the adsorbent features. This patent also does not utilize a particle of the instant invention. Adsorbent particles of the prior art have not achieved the ability to remove particular contaminants from a liquid or gas stream, such as, for example, a waste stream or drinking water, to acceptably low levels. Additionally, the adsorbent particles of the prior art have not been able to bind tightly to particular contaminants so that the adsorbent particle/contaminant composition can be safely disposed of in a landfill. Thus, there has been a need in the art for adsorbents that have improved ability to adsorb particular materials, particularly contaminants from a gas or liquid stream, to thereby purify the stream. There has been a need in the art for the adsorbent particles to tightly bind to the adsorbed contaminant. Applicants have discovered that acid enhanced particle solves the above problems in the art.

U.S. Patent No. 5,422,323 to Banerjee et al. discloses the preparation of a pumpable refractory insulator composition. The composition consists of the combination of a wet component of colloidal silica (40%) in water, and a dry component consisting of standard refractory material. Examples of refractory material include clay, kaolinite, mullite, alumina and alumina silicates. The resulting insulating composition was cast into shape, dried and baked to form an insulating layer.

Japanese Patent No. 63264125 to Furnikazu et al. discloses the preparation of dry dehumidifying materials. Moisture is removed from room air or gas as it passes through a dehumidifying rotor of zeolite (70% by weight) and an inorganic binder (2-30% by weight). The inorganic binder includes colloidal silica, colloidal alumina, silicates, alu inates and bentonite. Wet air was passed through the dehumidifying rotor, and the amount of dried air was assessed.

Japanese Patent No. 60141680 to Kanbe et al. discloses the preparation of a refractory lining repair material. The material was prepared by adding a solution of phosphoric acid with ultra fine silica powder to a mixture of refractory clay and refractory aggregates composed of grog, alumina, silica, zircon and pyrophyllite. The refractory material has improved bonding strength and minute structure, and are useful for molten metal vessels such as ladles, tundishes, and electric furnaces. Adsorbent particles of the prior art have not achieved the ability to remove particular contaminants from a liquid or gas stream, such as, for example, a waste stream or drinking water, to acceptably low levels. Additionally, the adsorbent particles of the prior art have not been able to bind tightly to particular contaminants so that the adsor- bent particle/contaminant composition can be safely disposed of in a landfill. Thus, there has been a need in the art for adsorbents that have improved ability to adsorb particular materials, particularly cont-tminants from a gas or liquid stream, to thereby purify the stream. There has been a need in the art for the adsorbent particles to tightly bind to the adsorbed contaminant. Also, there has been a need in the art for catalysts that have the ability or that have an improved ability to catalyze the reaction of contaminants into non-contaminant by-products.

Typically in the art, binders block active sites on the adsorbent and catalyst particles, thereby reducing the efficiency of such particles. Therefore, there is a need in the art for a binder system that binds adsorbent and/or catalytic particles together without reducing the performance of the particles.

Applicants have discovered that by using a special binder for adsorbent and/or catalytic particles, improved or new adsorbent and/or catalytic properties can be achieved due to the synergy between the binder and adsorbent and/or catalyst particle.

None of the above-cited documents discloses the compositions or processes such as those described and claimed herein.

SUMMARY OF THE INVENTION

In accordance with the purpose(s) of this invention, as embodied and broadly described herein, this invention, in one aspect, relates to a process for producing an enhanced adsorbent particle comprising contacting a non-amorphous, non-ceramic, crystalline, porous, calcined, aluminum oxide particle that was produced by calcining at a particle temperature of from 300° C to 700° C, with an acid for a sufficient time to increase the adsorbent properties of the particle.

The invention further provides a process for producing an enhanced adsorbent particle comprising contacting a non-ceramic, porous, oxide adsorbent particle with an acid for a sufficient time to increase the adsorbent properties of the particle.

In yet another aspect, the invention provides for particles made by the process of the instant invention.

In yet another aspect, the invention provides for a process for reducing or eliminating the amount of cont--minants in a stream comprising contacting the particle of the invention with the stream for a sufficient time to reduce or eliminate the contamination from the stream.

In still yet another aspect, the invention provides a composition comprising the particles of the invention.

In another aspect, the invention relates to a method for producing an adsorbent and/or catalyst and binder system comprising i) mixing components comprising a) a binder comprising a colloidal metal oxide or colloidal metalloid oxide, b) an oxide adsorbent and/or catalyst particle, and c) an acid, ii) removing a sufficient amount of water from the mixture to cross-link components a and b to form an adsorbent and/or catalyst and binder system.

In another aspect, the invention provides for an adsorbent and/or catalyst system made by the processes of the invention.

In one aspect, the invention provides an adsorbent and/or catalyst and binder system comprising a binder that has been cross-linked with at least one type of oxide adsorbent and/or catalyst particle.

In yet another aspect, the invention provides a method for reducing or eliminating the amount of a contaminant from a liquid or gas stream comprising contacting the adsorbent and/or catalyst binder system with the contaminant in the stream for a suffi- cient time to reduce or eliminate the amount of contaminant from the stream.

In yet another aspect, the invention provides a method for catalyzing the degradation of an organic compound comprising contacting the organic compound with the adsorbent and/or catalyst system for a sufficient time to catalyze the degradation of an organic compound.

In yet another aspect, the invention provides a method for reducing or eliminating the amount of a contaminant from a gas stream by catalysis comprising contacting the adsorbent and/or catalyst binder system with a gas stream containing a contami- nant comprising an oxide of nitrogen, an oxide of sulfur, carbon monoxide, hydrogen sulfide, or mixtures thereof for a sufficient time to reduce or eliminate the contaminant amount.

In yet another aspect, the invention provides a method for producing an adsorbent and/or catalyst and binder system comprising i) mixing components comprising a) a binder comprising a colloidal metal oxide or colloidal metalloid oxide, b) a first adsorbent and/or catalyst particle that does not cross-link with the binder, and c) an acid, ii) removing a sufficient amount of water from the mixture to cross-link component a to itself, thereby entrapping and holding component b within the cross-linked binder, to form an adsorbent and/or catalyst and binder system.

In another aspect the invention relates to a composition for binding adsorbent and/or catalytic particles to produce an agglomerated particle comprising (a) a colloidal metal oxide or colloidal metalloid oxide and (b) an acid.

In another aspect the invention relates to a kit for binding adsorbent and/or catalytic particles to produce an agglomerated particle comprising (a) a colloidal metal oxide or colloidal metalloid oxide and (b) an acid.

In yet another aspect, the invention provides a method for binding adsorbent and/or catalytic particles, comprising the steps of:

(a) mixing colloidal alumina or colloidal silica with the particles and an acid;

(b) agitating the mixture to homogeneity; and

(c) heating the mixture for a sufficient time to cause cross-linking of the aluminum oxide in the mixture.

In still yet another aspect, the invention relates to an adsorbent and/or catalyst and binder system, comprising:

(a) a pendant ligand substituted or unsubstituted binder, and (b) a pendant ligand substituted or unsubstituted oxide adsorbent and/or oxide catalyst particle, wherein at least one of components (a) and (b) is pendant ligand substituted, and wherein component (a) is cross-linked with component (b).

In another aspect, the invention relates to a method of using the above system as a catalyst and/or adsorbent support system comprising binding the above system with a second catalyst particle.

In still yet another aspect, the invention relates to an anchored adsorbent and/or catalyst and binder system, comprising: (a) a pendant ligand substituted or unsubstituted binder, and

(b) a pendant ligand substituted or unsubstituted oxide adsorbent and/or oxide catalyst particle, and

(c) a metal complex, wherein at least one of components (a) and (b) is pendant ligand substituted, wherein component (a) is cross-linked with component (b), and wherein the metal complex (c) is bound to component (a) and/or (b).

In still yet another aspect, the invention relates to a method for producing a pendant hgand substituted adsorbent and/or catalyst system, comprising: (i) mixing components, comprising:

(a) a pendant ligand substituted or unsubstituted binder comprising a colloidal metal oxide or a colloidal metalloid oxide,

(b) a pendant ligand substituted or unsubstituted oxide adsorbent and/or oxide catalyst particle, and (c) an acid, wherein at least one of components (a) and (b) is pendant ligand substituted, and (ii) removing a sufficient amount of water from the mixture to cross-link components (a) and (b) to form a pendant hgand substituted adsorbent and/or catalyst and binder system. This method can further comprise (iii) binding a metal complex onto the resulting system of step (ii) to form the anchored catalyst syste

In still yet another aspect, the invention relates to a method for producing an adsorbent and/or catalyst and binder system comprising

(i) mixing components comprising

(a) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,

(b) an oxide adsorbent and/or catalyst particle, and (c) an acid,

(ii) removing a sufficient amount of water from the mixture to cross-link components a and b to form an adsorbent and/or catalyst and binder system, and iii) reacting the resultant oxide adsorbent and/or oxide catalyst particle and the binder system of step (ii) with a hydroxyl-reactive compound to form a pendant ligand substituted oxide adsorbent and/or oxide catalyst and binder system.

In another aspect, the invention relates to the above method further comprising after step (iii) binding a metal complex onto the resulting system of step (iii) to form an anchored catalyst system.

In another aspect, the invention relates to an anchored adsorbent and/or catalyst and binder system, comprising: (a) a binder, and

(b) an oxide adsorbent and/or oxide catalyst particle, and

(c) a metal complex, wherein component (a) is cross-linked with component (b), and wherein the metal complex (c) is bound directly to component (a) and/or (b). In still yet another aspect, the invention relates to a method for producing an anchored adsorbent and/or catalyst system, comprising: (i) mixing components, comprising:

(a) a binder comprising a colloidal metal oxide or a colloidal metalloid oxide,

(b) an oxide adsorbent and/or oxide catalyst particle, and

(c) an acid,

(ϋ) removing a sufficient amount of water from the mixture to cross-link components (a) and (b) to form an adsorbent and/or catalyst and binder system, and

(iii) binding a metal complex directly onto the resulting system of step (ii) to form the anchored catalyst system

In another aspect, the invention relates to a method of encapsulating a contaminant within an adsorbent particle comprising heating the particle of the invention that has adsorbed a contaminant to a temperature sufficient to close the pores of the particle to thereby encapsulate the contaminant within the particle.

In another aspect, the invention relates to a method for regenerating the adsorbent particle that has adsorbed a contaminant.

Additional advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. BRIEF DESCRIPTION OF THE FIGURES

Fig. 1 is a graph showing the reduction in concentration of lead ions using a particle of the invention.

Fig. 2 is a graph showing surface area vs curing temperature of alurrma-alumina composites.

Fig. 3 is a graph showing the oxidation of CO over time using QiO/Mi- J L g- colloidal alumina binder coparticle.

Fig. 4 is a graph showing the reduction of NOx over time using CuO/Ga₂O₃/Al₂O₃- colloidal alumina binder coparticle.

DETAILED DESCRIPTION

The present invention may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the Examples included therein.

Before the present compositions of matter and methods are disclosed and described, it is to be understood that this invention is not limited to specific synthetic methods or to particular formulations, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings:

The singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise.

"Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

The term "particle" as used herein is used interchangeably throughout to mean a particle in the singular sense or a combination of smaller particles that are grouped together into a larger particle, such as an agglomeration of particles.

The term "ppm" refers to parts per million and the term "ppb" refers to parts per billion. The term "and/or" in "adsorbent and/or catalyst" refers to a particle that either acts as a catalyst, an adsorbent, or can act as both an adsorbent and catalyst under different circumstances due to, for example, the composition and the type of contaminant.

I. ACIDENHANCED OXIDEADSORBENTAND/ORCATALYSTPARTICLE

In accordance with the purpose(s) of this invention, as embodied and broadly described herein, this invention, in one aspect, relates to a process for producing an enhanced adsorbent particle comprising contacting a non- amorphous, non-ceramic, crystalline, porous, calcined, aluminum oxide particle that was produced by calcining at a particle temperature of from 300° C to 700° C, with an acid for a sufficient time to increase the adsorbent properties of the particle. This process can also consist essentially of or consist of the particular process steps as described above or further including the additional features described below.

The invention further provides a process for producing an enhanced adsorbent particle comprising contacting a non-ceramic, porous, oxide adsorbent particle with an acid for a sufficient time to increase the adsorbent properties of the particle. This process can also consist essentially of or consist of the particular process steps as described above or further including the additional features described below. In one embodiment, this particle is calcined.

I-n yet another aspect, the invention provides for particles made by the process of the instant invention.

In yet another aspect, the invention provides for a process for reducing or elirninating the amount of contaminants in a stream comprising contacting the particle of the invention with the stream for a sufficient time to reduce or eliminate the contamination from the strea

The particles of this invention have improved or enhanced adsorptive features. The particles of this invention can adsorb a larger amount of adsorbate per unit volume or weight of adsorbent particles than a non-enhanced particle. Also, the particles of this invention can reduce the concentration of contaminants or adsorbate material in a stream to a lower absolute value than is possible with a non-enhanced particle. In particular embodiments, the particles of this invention can reduce the contaminant concentration in a stream to below detectable levels, believed to be never before achievable with prior art particles. Enhanced adsorptive features is intended to particularly include ion capture and ion exchange mechanisms. Ion capture refers to the ability of the particle to irreversibly bind to other atoms by covalent or ionic interactions. In this invention, the ion capture typically predominates over the ion exchange property, and it is typically the improved ion capture property that improves the adsorbent performance of the particle. Adsorption is a term well known in the art and should be distinguished from absorption. The adsorbent particles of this invention chemically bond to and very tightly retain the adsorbate material. These chemical bonds are ionic and/or covalent bonds.

Not wishing to be bound by theory, it is believed that the acid contacting of the particle enhances the adsorptive capacity of the particle by increasing the number of hydroxyl groups on the particle. With cationic and anionic contaminants, the hydroxyl groups provide sites for chemical bonding or replacement, such that the contaminants bond irreversibly with the particle. In general, the increased amount of hydroxyl groups generate more active sites for the contaminant to bond with. The invention contemplates the use of any prior art adsorbent and/or catalyst particle or composite particle of two or more types of particles. In a preferred embodiment, the particle comprises an oxide particle, even more preferably a non-ceramic, porous oxide particle. The particle in one embodiment comprises a metal or metalloid oxide particle. Examples of such particles include, but are not limited to, oxide complexes, such as transition metal oxides, lanthanide oxides, thorium oxide, as well as oxides of Group IIA (Mg, Ca, Sr, Ba), Group IJJA (B, Al, Ga, In, Tl), Group IVA (Si,Ge, Sn, Pb), and Group NA (As, Sb, Bi). In another embodiment, the particle comprises an oxide of aluminum, titanium, copper, vanadium, silicon, manganese, iron, zinc, zirconium, tungsten, rhenium, arsenic, magnesium, thorium, silver, cadmium, tin, lead, antimony, rathenium, osmium, cobalt or nickel or zeohte. Typically, any oxidation state of the oxide complexes may be useful for the present invention. The oxide can be a mixture of at least two metal oxide particles having the same metal with varying stoichiometry and oxidation states. In one embodiment, the particle comprises Al₂O₃, TiO₂, CuO, Cu₂O, N₂O₅, SiO₂, MnO₂, Mn₂O₃, Mn₃O₄, ZnO, WO₂, WO₃, Re₂O₇, As₂O₃, As₂O₅, MgO, ThO₂, Ag₂O, AgO, CdO, SnO₂, PbO, FeO, Fe₂O₃, Fe₃O₄, Ru₂O₃, RuO, OsO₄, Sb₂0₃, CoO, Co₂O₃, ΝiO or zeohte. In a further embodiment, the particle further comprises a second type of adsorbent and/or catalyst particles of an oxide of alurriinum, titanium, copper, vanadium, silicon, manganese, iron, zinc, zirconium, tungsten, rhenium, arsenic, magnesium, thorium, silver, cadmium, tin, lead, antimony, rathemum, osmium, cobalt or nickel or zeolite, activated carbon, including coal and coconut carbon, peat, zinc or tin. In another embodiment, the particle further comprises a second type of adsorbent and/or catalyst particles of aluminum oxide, titanium dioxide, copper oxide, vanadium pentoxide, silicon dioxide, manganese dioxide, iron oxide, zinc oxide, zeohte, activated carbon, peat, zinc or tin particle. Typical zeohtes used in the present invention include "Y" type, "beta " type, rnordenite, and ZsM5. In a preferred embodiment, the particle comprises non-amorphous, non-ceramic, crystalline, porous, calcined aluminum oxide that was produced by calcining the precursor to the calcined aluminum oxide at a particle temperature of from 300 or 400 °C to 700 °C, preferably in the gamma, chi-rho, or eta form The precursor to calcined aluminum oxide can include but is not limited to boehrnite, bauxite, pseudo-boehmite, scale, Al(OH)₃ and du ina hydrates. In the case of other metal oxide complexes, these complexes can also be calcined or uncalcined.

In another embodiment of the invention, in the particle of this invention, typically any adsorbent particle that is non-ceramic, porous, is an oxide can be used. Some of the particles of this invention are in the crystalline form and are therefore non- amorphous. Adsorbent particles that are very rigid or hard, are not dissolved to any detrimental degree by the acid, and which have initially high, pre-enhanced adsorptive properties are preferred. Examples of such particles include, but are not limited to, metal oxides, such as transition metal oxides and Group IIA, Group IIIA, and Group INA metal oxides (CAS Group notation), and oxides of non-metals such as silicon and germanium. Preferred adsorbents include oxides of -duminum, silicon, including zeohtes, both natural and synthetic, manganese, copper, vanadium, z comurn, iron, and titanium. Even more preferred adsorbents include aluminum oxide (Al₂O₃), silicon dioxide (S ^, manganese oxides (MnO, MnO₂, Mn₂O₃, and Mn₃0₄), copper oxides (CuO and Cu₂0), vanadium pentoxide (V₂O₅), zirconium oxide (Zrθ₂), ^^on oxides (FeO, Fe₂0₃, and Fe₃O₄), and titanium dioxide (TiO₂). In a preferred embodiment, the particle is microporous, even more preferably substantially icroporous, having a median micropore size preferably of from 3.5 nm to 35 nm (35 A to 350 A) diameter.

In an even more preferred embodiment, the oxide is -duminum oxide (Al₂O₃) that has been produced by calcining at a particle temperature of from 300 °C to 700 °C. In other embodiments, the lower limit of calcining temperature is 400 °C, 450° C, 500° C, 550° C, 600° C, or 650° C and the upper limit is 650° C, 600° C, 550° C, 500° C, or 450° C. These preferred duminum oxide particles are preferably in the gamma, chi- rho, or eta forms. The ceramic form of Al₂O₃, such as the alpha form, are not included as a part of this invention. In a preferred embodiment, the Al₂O₃ particles of this invention are substantiahy microporous, having a median micropore size of from 3.5 nm to 35 or 50 nm diameter, even more preferably 60 nm, and a BET surface area of

In one embodiment, the particle is duminum oxide that has been pre-treated by a_calcination process. Calcined aluminum oxide particles are well known in the art. They are particles that have been heated to a particular temperature to form a particular crystalline structure. Processes for making calcined aluminum oxide particles are well known in the art as disclosed in, e.g., Physical and Chemical Aspects of Adsorbents and Catalysts, ed. Linsen et al, Academic Press (1970), which is incorporated by reference herein. In one embodiment, the Bayer process can be used to make aluminum oxide precursors. Also, pre-calcined aluminum oxide, that is, the aluminum oxide precursor (e.g., Al(OH)₃ or aluminum trihydrate, boebmite, pseudo-boebmite, bauxite), and calcined -duminum oxide are readily commercially available. Calcined aluminum oxide can be used in this dried, activated foπn or can be used in a partially or near folly deactivated form by allowing water to be adsorbed onto the surface of the particle. However, it is preferable to minimize the deactivation to maximize the adsorbent capability. In some references in the prior art, "activated" refers only to the surface water being removed from the particle to increase its adsorbent ability. However, as used in reference to the instant invention, "activated" oxide particles refer to an oxide particle that has first been calcined and is then also preferably but not necessarily maintained in its dried state. Thus, as used herein, all active particles of the invention have also been calcined. The particles are not limited to any physical form and can be in the particulate, powder, granular, pellet, or the like for

In another embodiment, in addition to being acid enhanced, the adsorbent, catalyst, and adsorbent and catalyst particles used in this invention can be enhanced by other processes known in the art or described below. For example the particles can be dried to be activated or can be treated by processes disclosed in U.S. Patent No. 5,955,393, issued on September 21, 1999, which is a continuation-in-part of PCT US96/05303, filed April 17, 1996, pending, which is a continuation-in-part of U.S. application serial No. 08/426,981, filed April 21, 1995, abandoned. This patent and applications are herein incorporated by this reference in their entireties for all of their teachings.

The acid that can be used in this invention can be any acid or mixture of acids that can catalyze the formation of hydroxyl groups onto the surface of the pores of the oxide particle. Examples of such acids include, but are not limited to, nitric acid, sulfuric acid, hydrochloric acid, boric acid, acetic acid, formic acid, phosphoric acid, and mixtures thereof. In one embodiment, the acid is an aliphatic or aromatic carboxylic acid. In another embodiment, the acid is acetic acid. Examples of aliphatic and aromatic carboxylic acids include but are not limited to acetic acid, benzoic acid, butyric acid, citric acid, fatty acids, lactic acid, maleic acid, malonic acid, oxalic acid, salicylic acid, stearic acid, succinic acid, tartaric acid, propionic acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, trideconoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, triosanoic acid, lignoceric acid, pentacosanoic acid, cerotic acid, heptasauoic acid, montanic acid, nonacosanoic acid, mehssic acid , phthahc acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, cinna ic acid, acrylic acid, crotonic acid, linoleic acid or a mixture thereof. In a preferred embodiment, the acid is acetic acid because it is relatively safer to handle than most other acids and because of its cost effectiveness.

Typically the acid is diluted with water to prevent dissolution of the particle and for cost effectiveness. In general, only a dilute solution of the acid is required to achieve maximum or saturated loading of the ion moieties on the particle. For example, a 0.5 wt. % (0.09 N; pH of about 2.9) and even a 0.1 wt. % (0.02 N; pH of about 3.25) acetic acid solution has been found effective. However, a wide range of concentrations of acid can be used in this invention from very dilute to very concentrated depending on the hazards involved and the economics of production. However, if the acid is too concentrated, it will etch the particle causing an increase in macropores while ehminating micropores, which is detrimental to the particles of this invention. Thus, the acid treatment is preferably of a concentration (i.e. acid strength as measured by, e.g., normality or pH), acid type, temperature and length of time to be more than a mere surface wash but less than an etching. In particular embodiments, the etching of the particle is rriiniiriized or is only nominal by selection of the acid treatment conditions, such as acid strength, acid type, and temperature and time of treatment, such that the reduction in overall surface area, as preferably measured by the BET method, is less than 20%, less than 15%, less than 10%, less than 5%, less than 2%, less than 1%, or less than 0.5%. Strong acids, such as for example hydrochloric, nitric or sulfuric, should preferably be used at a concentration or strength lower than a weak acid, such as for example acetic acid, because the strong acid tends to chemically react with and etch the particle to a much greater degree than a weak acid of comparable concentration.

In a particular embodiment, the acid is of an upper strength equivalent to a 0.5 N (noimality) aqueous solution of acetic acid. In other embodiments, the upper strength of the acid is equivalent to a 0.25 N, 0.1 N, 0.09 N, 0.075 N, 0.05 N, 0.02 N, 0.01 N, 0.005 N or 0.001 N aqueous acetic acid solution. The lower strength of the acid should be that which provides more than a surface washing but imparts enhanced adsorbent effects to the particle. In particular embodiments, the lower strength of the acid is equivalent to a 0.25 N, 0.1 N, 0.09 N, 0.075 N, 0.05 N, 0.02 N, 0.01 N, 0.005 N, 0.001 N, 0.0005 N, or 0.0001 N aqueous acetic acid solution.

After acid treatment, the resultant particle of the invention substantially retains the micropores originally present and the acid does not etch the particle to any appreciable degree and does not create any appreciable amount of new macropores (median pore diameter greater than about 35 nm). In a preferred embodiment, when the particle is aluminum oxide, the acid treated aluminum oxide maintains its microporous nature, having a median pore size of 3.5 nm to 35 nm diameter and a BET surface area of from l20 to 350 m²/g.

Additionally, the acid preferably has some water present to provide OH^" and/or H⁺ ions, which bond with the particle. When the acid is diluted with water, the water is preferably distilled water to minimize the amount of impurities contacting the particle.

The particle of the invention is made by the following process. The particle is contacted with an acid. The particle can be contacted with the acid by various means including by the particle being dipped in, extensively washing with, or submerged in the acid. The length of time the particle must be contacted with the acid varies according to the ability of the particular particle to generate hydroxyl groups on the surface and pores of the particle. The time can be as low as 30 seconds, a few (three) minutes, at least 15 minutes, at least one hour, at least 6 hours, at least 12 hours, or at least one day, to achieve adequate adsorption results and/or to preferably assure saturation. The time must be sufficient to at least increase the adsorbent properties of the particle by adding increasing the number of hydroxyl groups on the particle. In one embodiment, the particle is submerged in the acid, and saturation is typically complete when is full adsorption of the alumina pores with the acid solution. The contacting should be substantial enough to provide penetration of the acid throughout the pores of the particle thereby increasing the number of hydroxyl groups on the pore surface of the particle. Mere washing the outside surface of the particle to remove impurities is not sufficient to provide adequate penetration of the acid into and throughout the pores of the particle. Typically, the acid contacting is preformed at room temperature. The higher the acid temperature and concentration, the more likely the acid will detrimentally etch the particle.

The acid contacted particle is then optionally rinsed, preferably with water.

Rinsing of the acid contacted particle does not reduce the enhanced adsorptive capability of the particle. When rinsed, the particle is preferably rinsed with distilled water to rr-rnimize impurity contact. Rinsing of the particle serves two purposes. First, any residual acid that is remaining on the surface or pores of the particle is removed, which win make the particle easier to handle when it is in the dry for Second, rinsing the particle will remove the counter-ion of the acid that may be on the surface or pores of the particle.

Optionally, the particle is dried by a low to moderate heat treatment to remove excess liquid, such as acid or water, from the rinsing step to thereby increase the activity of adsorption. Typically, the drying is from about 50° C to about 200 °C. Drying of the particle also reduces the transfer cost of particle. However, the particle is preferably not calcined or recalcined after acid treatment and prior to contacting with a contaminant. Such recalcining would detrimentally change the surface characteristics by closing up the micropores. However, the particle can be heated to calcining temperatures or above after the particle has been contacted with a contaminant for encapsulating the contaminant as described below. Additionally, the particles of the invention are preferably not sintered, either before or after the acid treatment step, as this would detrimentally affect the micropores by closing up the micropores and would detrimentally decrease the pore volume and surface area. Any other process, such as a heat treatment, that would increase the size or eliminate micropores, enlarge the size of, create or destroy macropores, or would decrease the surface area available for adsorption or catalysis should preferably be avoided, particularly, after the particle is acid treated. The size of the particles used in this invention can vary greatly depending on the end use. Typically, for adsorption or catalytic apphcations, a small particle size such as 20 μm is preferable because they provide a larger surface area per unit volume than large particles. Typically for adsorption or catalytic apphcations, the particle size range is from 50 μm to 5000 μm.

The particle of this invention can be used in any adsorption or ion capture application known to those of ordinary skill in the art. In one embodiment, the particle is used for environmental remediation applications. In this embodiment, the particle can be used to remove contaminants, such as, but not limited to, heavy metals, organics, including hydrocarbons, chlorinated organics, including chlorinated hydrocarbons, inorganics, or mixtures thereof. Specific examples of cont-iminants include, but are not limited to, acetone, microbials such as crypto sporidium, ammonia, benzene, chlorine, dioxane, ethanol, ethylene, formaldehyde, hydrogen cyanide, hydrogen sulfide, methanol, methyl ethyl ketone, methylene chloride, propylene, styrene, sulfur dioxide, toluene, vinyl chloride, arsenic, lead, iron, phosphates, selenium, cadmium, uranium, such as U₃0₈, radon, l,2-dϊbromo-3-chloroρropane (DBCP), chromium, tobacco smoke, cooking fumes, zinc, trichloroethylene, and PCBs. The particle can remediate an anion, an oxoanion, a cation, or a poly-oxo anion. The particle of this invention can remediate individual contaminants or multiple contaminants from a single source. In essence, anywhere adsorbents are used to capture pollutants, this invention achieves improved efficiency by adsorbing a higher amount of contaminants and by reducing the contamination level to a much lower value than by non-enhanced particles.

For environmental remediation apphcations, particles of the invention are typically placed in a container, such as a filtration unit. The contaminated stream enters the container at one end, contacts the particles within the container, and the purified stream exits through the other end of the container. The particles contact the contaminants within the stream and bond to and remove the contamination from the stream. Typically, the particles become saturated with contaminants over a period of time, and the particles must be removed from the container and replaced with fresh particles. The contaminant stream can be a gas stream or liquid stream, such as an aqueous stream. The particles can be used to remediate, for example, waste water, production facility effluent, smoke stack gas, auto exhaust, drinking water, and the like.

The particle of the invention can be used alone, in combination with other particles prepared by the process of the invention, and/or in combination with other adsorbent, catalytic, or contaminant remediation particles known in the art. The particles can be combined in a physical mixture or agglomerated using techniques known in the art, such as with a binder, to form a m tifunctional composite particle.

The particle/binder system of the invention can be used preferably as the adsorbent or catalytic medium itself. In an alternate embodiment, the system is used as an adsorbent or catalytic support.

In one embodiment, the acid enhanced particle is used in combination with a particle that has been pretreated to improve its adsorbent and/or to improve or impart catalyst properties, such as an ion or electron enhancement, in accordance with U.S. Patent No. 5,955,393, issued on September 21, 1999, which is a continuation-in-part of PCT/US96/05303, filed April 17, 1996, pending, which is a continuation-in-part of U.S. patent application Serial No. 08/426,981, filed April 21, 1995, abandoned, all of which are herein incorporated by this reference for all of its teachings.

In another embodiment, the acid enhanced particle of the invention is used in combination with a noble metal known in the art for adsorbent or particularly catalytic properties. Such noble metals include gold, silver, platinum, paEadium, Mdium, rhenium, rhodium, cobalt, copper, ruthenium, and osmium, preferably gold, silver platinum, and palladium Such a combination can be used to take advantage of the adsorbent properties of the acid enhanced particle and the catalytic properties of the noble metal.

In one embodiment, the invention is directed to a composition comprising an aluminum oxide particle made by the acid enhancing process of the invention. In a further embodiment, this composition further comprises a co-particle. This co-particle is preferably any adsorbent or catalyst particle known in the art. Such co-particles can be preferably non-ceramic, porous, oxide adsorbent particles or activated carbon, more preferably silicon dioxide, or a metal oxide, such as manganese oxides (MnO, Mn0₂, Mn₂O₃, and Mn₃O₄), copper oxides (CuO and Cu^O), vanadium pentoxide (N₂O₅), zirconium oxide (ZrO^, iron oxides (FeO, Fe₂O₃, and Fe₃O₄), titanium dioxide ( -O₂) and zeohtes, both natural and synthetic and activated carbon. The co-particle can be acid-enhanced or non-acid enhanced. In a preferred embodiment, the co-particle is not initially acid-enhanced although it may be contacted with acid during the binding step.

In a preferred embodiment, the composition comprises aluminum oxide made by the acid enhanced process of the invention, copper oxide, and manganese oxide. Preferably, these components are in a proportion of from 50-98 parts by weight, more preferably 80-95 parts by weight, even more preferably 88 parts by weight acid enhanced aluminum oxide; and 1-49 parts by weight, more preferably 4-19 parts by weight, even more preferably 6 parts by weight of each of copper oxide and manganese oxide. Preferably, the copper oxide is CuO and the manganese oxide is Mn0₂. Preferably, the composition is held together using a colloidal alumina binder that has been crosshnked as described below. In a preferred embodiment, this composition can be used to remediate organics, including but not limited to hydrocarbons and chlorinated organics, even more preferably, trichloroethylene (TCE).

Not wishing to be bound by theory, it is believed that at least some and possibly all of the ability of the acid-enhanced aluminum oxide/co-particle embodiment of the invention described above to remediate organic cont--minants is due to a catalytic degradation of the organic contaminant, even at room temperature. This catalytic activity is evident because the inventive co-particle of Example 5 was challenged with a high concentration of organic contaminants and no organic contaminants were found the residual solution after TCLP analysis (see Example 6). In a preferred embodiment, the acid-enhanced Al₂O₃ in combination with one or more oxides of manganese, copper, and/or iron is particularly suited to catalytically degrade organics, such as hydrocarbons, chlorinated hydrocarbons and chlorinated organics, such as trichloroethylene. Even more preferably, the catalytic composition comprises 50-98 parts by weight, more preferably 80-95 parts by weight, even more preferably 88 parts by weight acid enhanced aluminum oxide; and 1-49 parts by weight, more preferably 4- 19 parts by weight, even more preferably 6 parts by weight of each of copper oxide and manganese oxide.

Binders for binding the individual particles to form an agglomerated particle are known in the art or are described herein. In a preferred embodiment, the binder can also act as an adsorbent and/or a catalyst.

A preferred binder that can be used with the particles of this invention is a cohoidal metal oxide or cohoidal metahoid oxide binder as disclosed in U.S. Patent No. 5,948,726, issued on September 7, 1999, which is (1) a continuation-in-part of PCT/US96/05303, filed April 17, 1996, pending, which is a continuation-in-part of U.S. apphcation serial No. 08/426,981, filed April 21, 1995, abandoned; (2) a continuation-in-part of U.S. apphcation serial No. 08/426,981, filed April 21, 1995, abandoned; (3) a continuation-in-part of U.S. apphcation serial No. 08/662,331, filed June 12, 1996, pending, which is a continuation-in-part of PCT/US95/15829, filed June 12, 1995, pending, which is a continuation-in-part of U.S. apphcation serial No. 08/351,600, filed December 7, 1994, abandoned; and (4) a continuation-in-part of PCT/US95/15829, filed June 12, 1995, pending, which is a continuation-in-part of U.S. apphcation serial No. 08/351,600, filed December 7, 1994, abandoned. A of the above apphcations and patent are hereby incorporated by this reference in their entireties for ah of their teachings. This cohoidal metal oxide or cohoidal metahoid oxide binder and binder system is also described in detail below in the following section II.

Additionally, this cohoidal metal oxide or cohoidal metahoid oxide binder can be used with an untreated (non-acid enhanced) particle of this invention and/or an acid treated (acid enhanced) particle of this invention described above in section I. This binder can be used on any of the particle compositions of this invention referred to above or below, whether acid enhanced or not. Additionally, the particles and systems described below under section II and section III can be untreated or acid treated (acid enhanced) as described above in section I.

A preferred binder for the agglomerated particle is cohoidal alumina or cohoidal silica. The cohoidal alumina goes through a transformation stage and cross-links with itsehfrom25°C to 400°C, preferably 250°C and/or can cross-link with the particle. Cohoidal silica cross-links with itself if it is sufficiently dried to remove water typicahy at temperatures of from 25° C to 400 °C. Preferably, from about 1 to 99.9 by weight, 20% to 99% or 10 to 35% by weight of the total mixture is cohoidal -ύumina or cohoidal silica to provide the necessary crosslinking during heating to bind the agglomerated particle into a water-resistant particle. The particle can then withstand exposure to ah types of water for an extended time and not disintegrate.

The binder can be mixed with the particle before or after the acid treatment of this invention. In one embodiment, the agglomerated particle is made by mixing cohoidal alumina with the adsorbent particles. Typicahy, from about 1 to about 99.9% by weight, 10 to 35% by weight, or from 20 to 99% by weight of the mixture is cohoidal -humina. In one embodiment, the particle mixture is then mixed with an acid solution such as, for example, nitric, sulfuric, hydrochloric, boric, acetic, formic, phosphoric, and mixtures thereof. In one embodiment the acid is 5% nitric acid solution. In another embodiment, the acid is an aliphatic or aromatic carboxylic acid. In a preferred embodiment, the acid is acetic acid. The cohoidal alumina and adsorbent and/or catalytic particles are thoroughly mixed so as to create a homogenous blend of ah elements. The additional acid solution is added and further mixing is performed until the mixture reaches a suitable consistency for agglomeration. After agglomeration is complete, the agglomerated particles are heated or dehydrated to cause the cohoidal alumina crosslinking to occur.

The particle of this invention bonds with the contaminant so that the particle and contaminant are tightly bound. This bonding makes it difficult to remove the cont-iminant from the particle, allowing the waste to be disposed of into any public landfill. Measurements of contaminants adsorbed on the particles of this invention using an EPA Toxicity Characteristic Leachabihty Procedure (TCLP) test known to those of skill in the art showed that there was a very strong interaction between the particles of this invention and the contaminants such that the contaminant is held very tightly.

II. BINDER AND OXIDE ADSORBENT AND/OR OXIDE CATALYST

SYSTEM

In accordance with the purpose(s) of this invention, as embodied and broadly described herein, this invention, in one aspect, relates to a method for producing an adsorbent and/or catalyst and binder system comprising i) mixing components comprising a) a binder comprising a cohoidal metal oxide or cohoidal metahoid oxide, b) an oxide adsorbent and/or catalyst particle, and c) an acid, ii) removing a sufficient amount of water from the mixture to cross-link components a and b to form an adsorbent and/or catalyst and binder system.

In yet another aspect, the invention provides a method for reducing or eliminating the amount of a contaminant from a hquid or gas stream comprising contacting the adsorbent and/or catalyst binder system with the contaminant in the stream for a sufficient time to reduce or eliminate the amount of contaminant from the stream.

In yet another aspect, the invention provides a method for reducing or eliminating the amount of a cont-uninant from a gas stream by catalysis comprising contact- ing the adsorbent and/or catalyst binder system with a gas stream containing a contaminant comprising an oxide of nitrogen, an oxide of sulfur, carbon monoxide, hydrogen sulfide, or mixtures thereof for a sufficient time to reduce or eliminate the contaminant amount. In yet another aspect, the invention provides a method for producing an adsorbent and/or catalyst and binder system comprising i) mixing components comprising a) a binder comprising a cohoidal metal oxide or cohoidal metahoid oxide, b) a first adsorbent and/or catalyst particle that does not cross-link with the binder, and c) an acid, ii) removing a sufficient amount of water from the mixture to cross-link component a to itself, thereby entrapping and holding component b within the cross-linked binder, to form an adsorbent and/or catalyst and binder syste

In another aspect the invention relates to a composition for binding adsorbent and/or catalytic particles to produce an agglomerated particle comprising (a) a cohoidal metal oxide or cohoidal metahoid oxide and (b) an acid.

In another aspect the invention relates to a kit for binding adsorbent and/or catalytic particles to produce an agglomerated particle comprising (a) a cohoidal metal oxide or cohoidal metahoid oxide and (b) an acid.

(a) mixing cohoidal alumina or cohoidal silica with the particles and an acid;

(b) agitating the mixture to homogeneity; and

(c) heating the mixture for a sufficient time to cause cross-linking of the -iluminum oxide in the mixture. When the system acts as an adsorbent, the adsorbent and binder system of this invention has improved or enhanced adsorptive features. In one embodiment, the system of this invention can adsorb a larger amount of adsorbate per unit volume or weight of adsorbent particles than a prior art system. In another embodiment, the adsorbent and binder system of this invention can reduce the concentration of contaminants or adsorbate material in a stream to a lower absolute value than is possible with a non-bound or prior art-bound particle. In particular embodiments, the adsorbent and binder system of this invention can reduce the contaminant concentration in a stream to below detectable levels. Adsorption is a term weh known in the art and should be distinguished from absorption. The adsorbent particles of this invention chemically bond to and very tightly retain the adsorbate material. These chemical bonds are ionic and/or covalent in nature.

The catalyst and binder system of the invention can also be used for the catalytic decomposition or remediation of contaminants. The catalyst system achieves improved catalytic performance or catalytic properties never seen before for a particulai' contaminant. The adsorbent and/or catalyst and binder system can be prepared by techniques set forth below to form a multifunctional composite particle. The catalysis can be at room temperature for certain apphcations.

The binder comprises an oxide particle that can react, preferably cross-link, with the other oxide complexes. This binder can also react, preferably cross-link, with itself. The binder forms cross-links with other oxide complexes upon drying by forming chemical bonds with itself and with other oxides. Under acidic conditions, the binder has a large number of surface hydroxyl groups. In one embodiment, the binder, which is designated as B-OH, cross-links with itself upon the loss of water to generate B-O-B. In addition to cross-linking with itself, the binder B-OH can also cross-link with an adsorbent and/or catalyst oxide complex (M-O), hydroxyl complex (M-OH), or a hydroxylated metal oxide to produce B-O-M. The adsorbent and/or catalyst complexes are referred to herein as oxide adsorbent and/or catalyst particles or oxide adsorbent and/or oxide catalyst particles, both intending that the particle, which can have adsorbent, catalytic, or adsorbent and catalytic properties, has an oxide and/or hydroxide complex. The resulting binder system consists of a three dimensional network or matrix wherein the component particles are bound together with B-O-B and B-O-M bonds. The resulting system can be used as an adsorbent and/or catalyst system. The resultant system is sometimes referred to as an agglomerated particle.

"Cohoidal metal or metahoid oxide (i.e. colloidal metal oxide or cohoidal metalloid oxide) binder" as defined herein means a particle comprising a metal or metahoid mixed hydroxide, hydroxide oxide or oxide particle, such that the weight loss from the cohoidal metal or metahoid oxide binder due to loss of water upon ignition is from 1 to 100%, 5 to 99%, 10 to 98%, or 50 to 95% of the theoretical water weight loss on going from the pure metal or metahoid hydroxide to the corresponding pure metal or metalloid oxide. The loss of water on going from the pure metal or metahoid hydroxide to the corresponding pure metal or metalloid oxide (e.g. the conversion of n M(OH)_x to MJO_m and y H₂O or more specifically from 2 Al(OH)₃ to Al₂O₃ and 3 H₂O) is defined as 100% of the water weight loss. Thus, the weight loss refers to loss of water based on the initial weight of water (not the total initial binder weight). There is a continuum of metal or metahoid hydroxides, hydroxide oxides, and oxides in a typical commercial product, such that, loss or removal of water from the metal or metahoid hydroxides produces the corresponding hydroxide oxides which upon further loss or removal of water give the corresponding metal or metahoid oxides. Through this continuum the loss or removal of water produces M-O-M bonds, where M is a metal or metahoid. The particles of this continuum, except for the pure metal or metalloid oxides, are suitable to serve as cohoidal metal or cohoidal oxide binders in this invention. In another embodiment, the binder system involves the use of a binder in combination with a particle with few or no surface hydroxyl groups, such that the particle does not cross-link or only nominahy cross-links with the binder. Examples of particles that posses only nominal amounts or that do not posses surface hydroxyl groups include particles of metals, such as, but not limited to tin or zinc, or carbon. In another embodiment, component b does not contain an oxide particle. Metal alloys such as bronze can also be used. In a preferred embodiment, the particle is activated carbon. In this embodiment, the binder cross-links with itself in a manner described above to form a three dimensional network or matrix that physically entraps or holds component b without cross-linking or cross-linking only to a very smah degree with component b. The resulting binder system can be used as an adsorbent and/or catalyst syste

In another embodiment, the invention is directed to a method for producing an adsorbent and/or catalyst and binder system comprising i) mixing components comprising a) a binder comprising a cohoidal metal oxide or cohoidal metahoid oxide, b) a first adsorbent and/or catalyst particle that does not cross-link with the binder, and c) an acid, ii) removing a sufficient amount of water from the mixture to cross-link component a to itself, thereby entrapping and holding component b within the cross-linked binder, to form an adsorbent and/or catalyst and binder system, further comprising a second adsorbent and/or catalyst particle that cross-links with the binder, thereby cross-linking the binder and the second particle and thereby entrapping and holding the first particle within the cross-linked binder and/or within the cross- linked binder and second particle. In this embodiment, the system comprises a binder and oxide adsorbent and/or catalyst particles that cross-links with the binder as well as particles that have a limited amount of surface hydroxyl groups, which do not cross-link with the binder. In this case, the binder cross links to itself and to the oxide complex particles, and the binder also forms a network or matrix around the particles that have a limited number of surface hydroxyl groups.

Binders that can be used in the present invention are cohoidal metal or metalloid oxide complexes. Cohoidal as used herein is defined as an oxide group that has a substantial number of hydroxyl groups that can form a dispersion in aqueous media. This is to be distinguished from the other use of the term cohoid as used in regard to a size of less than 1 μm. The binders herein are typicahy smah in size, e.g. less than 150 μm, but they do not have to be ah less than 1 μm Typically, the binder is un-calcined to maximize the hydroxyl group availability. Moreover, they must have a substantial number of hydroxyl groups that can form a dispersion in aqueous media, which is not always true of cohoid particles merely defined as being less than 1 μm. Examples of binders include but are not limited to any metal or metahoid oxide complex that has a substantial number of hydroxyl groups that can form a dispersion in aqueous media. In one embodiment, the binder is cohoidal alumina, cohoidal silica, cohoidal metal oxide where the metal is iron, or a mixture thereof, preferably cohoidal alumina or cohoidal sihca. In another embodiment the binder is not cohoidal alumina or cohoidal sihca. Cohoidal alumina can be a powder, sol, gel or aqueous dispersion. Cohoidal -ύu ina may be further stabilized with an acid, preferably nitric acid, acetic acid, or formic acid, and even more preferably 3 to 4% nitric acid. In a preferred embodiment, the cohoidal alumina is un-calcined with a sufficient number of hydroxyl groups such that the total particle weight loss (as distinguished from just water weight loss discussed above) upon ignition is between from 5% to 34%, more preferably from 20% to 31%. The cohoidal alumina size is preferably from 5 nm to 400 μm, preferably at least 30 wt% is less than 25 μm and 95 wt% is less than 100 μm. The cohoidal sihca is preferably un-calcined with a sufficient number of hydroxyl groups such that the total particle weight loss upon ignition is between from 5% to 37%, more preferably from 20% to 31%. The cohoidal sihca size is preferably from 5 nm to 250 μm, preferably at least 30 wt% is less than 25 μm and 95 wt% is less than 100 μm. In one embodiment, the binder is from 1% to 99.9% by weight of the mixture, preferably from 10% to 35% by weight. As used herein, the binder will be referred to as "cohoidal" to distinguish it from particle b, as the composition types can be the same, e.g. both can contain aluminum oxides.

Although prior art binders can be used in combination with the binder system of the present invention, these prior art binders lack certain advantages, ha the present invention, the activity is not degraded when exposed to aqueous solutions. The system is also very durable and not subject to falling apart when exposed to a waste stream, unlike other prior art adsorbent and/or catalyst and binder systems, such as polyvinyl pyrolidone, starch, or cellulose.

The invention contemplates the use of any prior art oxide adsorbent and/or catalyst particle or composite particle of two or more types of particles and binder system, but replacing the prior art binder with the binder of the present invention. In one aspect, the invention provides an adsorbent and/or catalyst and binder system comprising a binder that has been cross-linked with at least one type of oxide adsorbent and/or catalyst particles. In one embodiment, component b comprises at least two different types of oxide adsorbent and/or catalyst particles, to form a cross-linking between the binder and both particles to thereby form a composite particle. In another embodiment, component b comprises at least three different types of adsorbent and/or catalyst particles. In a preferred embodiment, component b comprises an oxide particle, preferably a metal oxide particle, and even more preferably a non-ceramic, porous metal oxide particle. Examples of such particles include, but are not limited to, oxide complexes, such as transition metal oxides, lanthanide oxides, thorium oxide, as weh as oxides of Group IIA (Mg, Ca, Sr, Ba), Group IIIA (B, Al, Ga, In, Tl), Group IVA (Si,Ge, Sn, Pb), and Group NA (As, Sb, Bi). In general, any oxide complex that is a basic anhydride is suitable for component b. In another embodiment, component b comprises an oxide of alummum, tit-uiium, copper, vanadium, silicon, manganese, iron, zinc, zirconium, tungsten, rhenium, arsenic, magnesium, thorium, silver, cadmium, tin, lead, antimony, ruthenium, osmium, cobalt or nickel or zeohte. Typicahy, any oxidation state of the oxide complexes may be useful for the present invention. The oxide can be a mixture of at least two metal oxide particles having the same metal with varying stoichiometry and oxidation states. In one embodiment, component b comprises Al₂O₃, Ti0₂, CuO, Cu NA, SiO₂, Mn0₂, Mn₂0₃, Mn₃O₄, ZnO, W0₂, WO₃, Re₂O₇, As₂O₃, As₂O₅, MgO, ThO₂, Ag₂O, AgO, CdO, Sn0₂, PbO, FeO, Fe₂0₃, Fe₃O₄, RuA, RuO, OsO₄, Sb₂0₃, CoO, Co₂O₃, ΝiO or zeohte. In a further embodiment, component b further comprises a second type of adsorbent and/or catalyst particles of an oxide of alummum, titanium, copper, vanadium, silicon, manganese, iron, zinc, zirconium, tungsten, rhenium, arsenic, magnesium, thorium, silver, cadmium, tin, lead, antimony, rathemum, osmium, cobalt or nickel or zeohte, activated carbon, including coal and coconut carbon, peat, zinc or tin. In another embodiment, component b further comprises a second type of adsorbent and/or catalyst particles of duminum oxide, titanium dioxide, copper oxide, vanadium pentoxide, silicon dioxide, manganese dioxide, iron oxide, zinc oxide, zeohte, activated carbon, peat, zinc or tin particle. Typical zeohtes used in the present invention include "Y" type, "beta " type, mordenite, and ZsM5. In a preferred embodiment, component b comprises non- amorphous, non- ceramic, crystalline, porous, calcined duminum oxide that was produced by cdcining the precursor to the cdcined duminum oxide at a particle temperature of from 300 or 400 °C to 700 °C, preferably in the gamma, chi-rho, or eta for The precursor to cdcined duminum oxide can include but is not limited to boehmite, bauxite, pseudo- boel ite, scde, Al(OH)₃ and du ina hydrates. In the case of other metd oxide complexes, these complexes can dso be cdcined or uncdcined.

The adsorbent and/or catdyst particles used in this invention can be unenhanced or enhanced by processes known in the art or described below. For example, the particles can be dried to be activated or can be of a composition or treated by ion or electron beam or acid activation or enhancement treatment processes disclosed in (1) U.S. Patent No. 5,955,393, issued on September 21, 1999, which is a continuation-in- part of PCT/US96/05303, filed April 17, 1996, pending, whichis a continuation-in-part of U.S. apphcation serid No. 08/426,981, filed April 21, 1995, abandoned, and (2) U.S. Patent No. 5,985,790, issued on November 16, 1999, which is a continuation-in- part of U.S. apphcation serid No. 08/662,331, filed June 12, 1996, abandoned, whichis a continuation-in-part of PCT/US95/15829, filed June 12, 1995, pending, which is a continuation-in-part of U.S. apphcation serid No. 08/351,600, filed December 7, 1994, abandoned, the disclosures of both patents and ah of their prior filed priority apphcations are herein incorporated by this reference in their entireties for ah of their teachings, including, but not limited to particle compositions and methods of treatment. The acid treatment or enhancement method and particles is described above in section I. In one embodiment the oxide adsorbent and/or catdyst particle has not been acid enhanced treated.

In one embodiment, an acid is used to cross-link the binder with component b. The addition of an acid to the binder facilitates or enables the reaction between the binder and the oxide particle. A strong or dilute acid can be used. A dilute acid is preferred to mirimize etching of certain particles. Typicahy the acid is dhuted with water to prevent dissolution of the particle and for cost effectiveness. The acid treatment is preferably of a concentration (ie. acid strength as measured by, e.g., normality or pH), acid type, temperature and length of time to cross-link the binder and component b.

In one embodiment, the acid comprises nitric acid, sulfuric acid, hydrochloric acid, boric acid, acetic acid, formic acid, phosphoric acid or mixtures thereof, preferably acetic acid or nitric acid. In another embodiment, the acid is an aliphatic or aromatic carboxylic acid. Examples of aliphatic and aromatic carboxylic acids include but are not limited to acetic acid, benzoic acid, butyric acid, citric acid, fatty acids, lactic acid, mdeic acid, mdonic acid, oxalic acid, salicylic acid, stearic acid, succinic acid, tartaric acid, propionic acid, vderic acid, hexanoic acid, heptanoic acid, capryhc acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, trideconoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, triosanoic acid, hgnoceric acid, pentacosanoic acid, cerotic acid, heptasauoic acid, montanic acid, nonacosanoic acid, mehssic acid , phthahc acid, glutaric acid, adipic acid, azeldc acid, sebacic acid, cinnarnic acid, acrylic acid, crotonic acid, hnoleic acid or a mixture thereof. In another embodiment, the concentration of the acid is from 0.15 N to 8.5 N, preferably from 0.5 N to 1.7 N. The volume of dilute acid used must be high enough so that the adsorbent and/or catdyst particle of the present invention can be used as is or further processed, such as extruded or filter pressed.

In another embodiment, a base can be used to cross-link the binder with component b. Any of the oxide adsorbent and/or catdyst particles described above can be used in this embodiment of the invention. The base that can be used in this invention can be any base or mixture of bases that can promote the formation of hydroxyl groups onto the surface of the support and/or the adsorbent and/or catdyst compound or precursor. Any base known in the art can be used to prepare the binder syste Examples of useful bases include, but are not limited to, LiOH, NaOH, KOH, RbOH, CsOH, Be(OH)₂, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, Ba(OH)₂, Bronsted bases, or Lewis bases such as, ammonia or pyridine in water. The concentration of the base will vary depending upon the selection of the binder and/or the oxide adsorbent and/or catdyst particle. In one embodiment, the concentration is from 0.1 to 0.5 N.

In another embodiment, the oxide adsorbent and/or catdyst particle is base treated prior to admixing with the binder. Ah of the oxide adsorbent and/or catdyst particles described above can be base treated. In another embodiment, the base is of an upper strength equivdent to a 0.5 N (normality) aqueous solution. In another embodiment, the base concentration is from 0.0001 N to 2 N. In other embodiments, the upper strength of the acid is equivdent to a 0.25 N, 0.1 N, 0.09 N, 0.075 N, 0.05 N, 0.02 N, 0.01 N, 0.005 N or 0.001 N aqueous solution. Any lower limit can be used with any upper hmit. The lower strength of the base should be that which provides more than a surface wasrrmg but imparts enhanced adsorbent effects to the metd oxide. In particular embodiments, the lower strength of the base is equivdent to a 0.25 N, 0.1 N, 0.09 N, 0.075 N, 0.05 N, 0.02 N, 0.01 N, 0.005 N, 0.001 N, 0.0005 N, or 0.0001 N aqueous solution. In one embodiment, the base concentration range is from 0.0001 N to 0.25 N, 0.0005 N to 0.09, 0.005 N to 0.075 N, or 0.01 N to 0.05 N.

In another embodiment, water can be used to prepare the binder syste In one embodiment, when the oxide adsorbent and/or catdyst particle is pretreated with an acid or a base to produce surface hydroxyl groups, then water can be used to facilitate cross-lir-king between the binder and the oxide adsorbent and/or catdyst particle. For example, any of the particles disclosed in U.S. Patent No. 5,985,790, and internationd pubhcation no. WO 97/47380 can be used in this embodiment of the invention. Any of the acid-treated or base-treated the oxide adsorbent and/or catdyst particles described above can be used in this embodiment of the invention.

In order to ensure efficient cross-linking between the binder and the oxide particle component, water is removed from the resulting binder syste This is typicahy performed by using a drying agent or heating the system. The cross-hhking temperature as used herein is the temperature at which cross-linking between the binder and the oxide adsorbent and/or catdyst component b occurs at an acceptable rate or the temperature at which the binder reacts with itself at an acceptable rate. In one embodiment, the cross-hhking temperature is from 25 °C to 400 °C. Thus, in one embodiment, the cross-hnking temperature for certain binders is at room temperature and requires no heating, dthough the rate of cross-linking at this temperature is slow. In various embodiments, the cross-linking temperature, and thus the heating step, is from50°C, 70°C, 110°C, or 150°C to 200°C, 250°C, 300°C, or 350°C, preferably 150°C to 300°C, even more preferably about 250°C. Ηie cross-liriking process can take place in open air, under an inert atmosphere or under reduced pressure. The cross- linking temperature can effect the activity of the adsorbent and/or catdyst and binder system. When cross-hnking occurs in the open air, then the particle is more susceptible to oxidation as the cross-lirdάng temperature is increased. Oxidation of the particle can ultimately reduce the activity of the particle.

Preferably, during or after step (i), the mixture of step (i) is not heated above the cross-linking temperature of the cohoidd metd oxide or cohoidd metahoid oxide. Preferably, during or after step (i), the mixture of step (i) is not heated to or above the cdcining temperature of the cohoidd metd oxide or cohoidd metahoid oxide. Preferably, during or after step (i), the mixture of step (i) is not heated to or above the cdcining temperature of the particle. In various embodiments, during or after step (i), the mixture of step (i) is not heated above 500° C, 450° C, 400° C, 350° C, 300° C, or 250° C, preferably not above 400°C. Cross-linking should be distinguished from cdcining. Cdcining typicahy involves heating a particle to remove any residud water that may be on the particle as weh as change the lattice structure of the particle to form a crystalline particle. For example for producing a crystalline duminum oxide particle, the cdcining temperature is about 300 or 400 °C to about 700 °C. Cdcining dso removes the hydroxyl groups on the binder that are required for cross-linking. Therefore, heating the system during or after step (i) above the cross-linking temperature into the particle or binder cdcining temperature range or above is detrimentd to the system. Thus, prior art systems, where mixtures of cohoidd dumina and/or cohoidd sihca are (1) cdcined or recdcined or (2) heated to form a refractory materid are not a part of this invention. In another aspect, the invention provides for an adsorbent and/or catdyst system made by the process of the invention.

The binder system of the invention is made in one embodiment by the following generd process. The (1) binder and (2) adsorbent and/or catdyst particles are pre- mixed in dry form. The cohoidd binder can be added or prepared in situ. For example, dum could be added as a dry powder and converted to cohoidd dumina in situ. Other duminum based compounds can be used for the in situ process, such as duminum chloride, duminum secondary butoxide, and the like. A solution of the acid is added to the mixture, and the mixture is stirred or agitated, typicahy from 1 minute to 2 hours, preferably from 10 minutes to 40 minutes, until the materid has a homogeneous "clay" like texture. The mixture is then ready for cross-linking or can be first fed through an extruder and then cut or chopped into a find shape, preferably spheres, pellets or saddles, typicahy of a size from 0.2 mm to 3 mm, preferably 0.5 to 1.5 mm. After the find shape is made, the product is transferred to a drying oven where they are dried from 15 minutes to 4 hours, preferably from 30 minutes to 2 hours. Once the binder is added to the adsorbent and/or catdyst particles (component b), the mixture is not heated to cdcine or recdcine the particle b or binder. Such cdcining or recdcining would detrimentally change the surface characteristics of component b by closing up the micropores. Additionally, the particles of the invention are preferably not sintered, as this would detrimentally affect the micropores by closing up the micropores and would detrimentally decrease the pore volume and surface area. The particles and binder system are dso not heated above the cdcining temperature to form a refractory materid. Any other process that would increase the size or eliminate micropores, enlarge the size of, create macropores at the expense of micropores or destroy macropores, or would decrease the surface area available for adsorption or catdysis should preferably be avoided. The size and shape of the particles used in this invention prior to extruding can vary greatly depending on the end use. Typicahy, for adsorption or catdytic apphcations, a smah particle size such as 5 μm or greater to about 250 μm are preferable because they provide a larger surface area than large particles.

In yet another aspect, the invention provides a method for reducing or ehmina- ting the amount of a contaminant from a hquid or gas stream comprising contacting the adsorbent and/or catdyst binder system with the contaminant in the stream for a sufficient time to reduce or eliminate the amount of contaminant from the stream. In one embodiment, the stream is a hquid, preferably water. In another embodiment, the stream is a gas, preferably comprising air or naturd gas.

The adsorbent and/or catdyst binder system of this invention can be used for environmentd remediation apphcations. In this embodiment, contaminants from a hquid or gas stream can be reduced or ehminated by a catdysis reaction. In another embodiment, contaminants from a hquid or gas stream can be reduced or eliminated by an adsorption reaction. The particle can be used to remove cont-m inants, such as, but not limited to, heavy metds, organics, including hydrocarbons, chlorinated organics, including chlorinated hydrocarbons, inorganics, or mixtures thereof. Specific examples of contaminants include, but are not limited to, acetone, ammonia, benzene, carbon monoxide, chlorine, hydrogen sulfide, trichloroethylene, 1,4-dioxane, ethanol, ethylene, formddehyde, hydrogen cyanide, hydrogen sulfide, methanol, methyl ethyl ketone, methylene chloride, oxides of nitrogen such as nitrogen oxide, propylene, styrene, oxides of sulfur such as sulfur dioxide, toluene, vinyl chloride, arsenic, cadmium, chlorine, 1,2-dibiOmochloropropane (DBCP), iron, lead, phosphate, radon, selenium, an anion, an oxoanion, a poly-oxoanion or uranium, such as U₃O₈. The adsorbent and/or catdyst binder system of this invention can remediate individud contaminants or multiple contaminants from a single source. This invention achieves improved efficiency by adsorbing a higher amount of contaminants and by reducing the contamination level to a much lower vdue than by non-enhanced particles.

In yet another aspect, the invention provides a method for catdyzing the degra- dation of an organic compound comprising contacting the organic compound with the adsorbent and/or catdyst system for a sufficient time to catdyze the degradation of an organic compound. In one embodiment, the catdysis reaction is at room temperature. In a one embodiment, the organic compound is a chlorinated organic compound, such as trichloro ethylene (TCE). In one embodiment, the catdyst and binder system catdyzes the hydrolysis of the chlorinated organic compounds.

In yet another aspect, the invention provides a method for reducing or eliminating the amount of a contaminant from a gas stream by catdysis comprising contacting the adsorbent and/or catdyst binder system with a gas stream containing a contaminant comprising an oxide of nitrogen, an oxide of sulfur, carbon monoxide, hydrogen sulfide, or mixtures thereof for a sufficient time to reduce or eliminate the contaminant amount. In one embodiment, the catdysis reaction is at room temperature.

For environmentd remediation apphcations, adsorbent and/or catdyst particles of the invention are typicahy placed in a container, such as a filtration unit. The contaminated stream enters the container at one end, contacts the particles within the container, and the purified stream exits through another end of the container. The particles contact the contaminants within the stream and bond to and remove the cont--mination from the stream. Typicahy, the particles become saturated with contaminants over a period of time, and the particles must be removed from the container and replaced with fresh particles. The contaminant stream can be a gas stream or hquid stream, such as an aqueous stream The particles can be used to remediate, for example, waste water, production facihty effluent, smoke stack gas, auto exhaust, drinking water, and the like. The particle/binder system of the invention can be used preferably as the adsorbent or catdytic medium itself. In an dternate embodiment, the system is used as an adsorbent or catdytic support. In another embodiment, it is not used as a catdyst support.

When the particle adsorbs a contaminant, the particle of this invention bonds with the contaminant so that the particle and contaminant are tightly bound. This bonding makes it difficult to remove the contaminant from the particle, allowing the waste to be disposed of into any pubhc landfill. Measurements of contaminants adsorbed on the particles of this invention using an EPA Toxicity Characteristic

Leachabihty Procedure (TCLP) test known to those of skill in the art showed that there was a very strong interaction between the particles of this invention and the cont- iinants such that the contaminant is held very tightly.

Although the particle system bonds tightly to the contaminant, the system of the invention can be regenerated by various techniques. In one embodiment, the acid enhanced particle of section I above can be regenerated. In another embodiment, the binder and oxide adsorbent and/or catdyst system can be regenerated. In one embodiment, the particle can be regenerated by roasting it in air to reoxidize the particle. In another embodiment, the contaminant can be removed by contacting the particle having the adsorbed contaminant with a reagent wash. The reagent wash can include but is not limited to aqueous ammonia, phosphines or detergents. In yet another embodiment, the use of a pH swing can remove the contaminant from the particle. Various pH ranges can be used to remove the contaminant form the particle depending upon the type of contaminant. In one embodiment, an acidic solution can be used to remove a cation from the particle. In another embodiment, a basic solution can be used to remove an anion from the particle. In another embodiment, Lewis acids and bases can be used to remove the contaminant from the adsorbent particle. In one embodiment, component b comprises duminum oxide, copper oxide, and manganese dioxide. In this embodiment, the binder is preferably cohoidd dumina. In this embodiment, the acid is preferably acetic acid. In this embodiment, the binder is from 1 to 97 parts by weight, preferably from 5 to 35 parts by weight, the duminum oxide is from 1 to 97 parts by weight, preferably from 55 to 85 parts by weight, the copper oxide is from 1 to 97 parts by weight, preferably from 1 to 20 parts by weight, and the manganese oxide is from 1 to 97 parts by weight, preferably from 1 to 20 parts by weight. In another embodiment, the binder is 20 parts by weight, duminum oxide is 70 parts by weight, copper oxide is 5 parts by weight, and manganese dioxide is 5 parts by weight.

In another embodiment, component b comprises durninurn oxide and activated carbon. In this embodiment, the binder is preferably cohoidd dumina. In this embodiment, the acid is preferably acetic acid. In this embodiment, the binder is from 1 to 98 parts by weight, preferably from 5 to 35 parts by weight, the duminum oxide is from 1 to 98 parts by weight, preferably from 45 to 75 parts by weight, and the activated carbon is from 1 to 98 parts by weight, preferably from 35 to 55 parts by weight. In another embodiment, the binder is 20 parts by weight, duminum. oxide is 60 parts by weight, and activated carbon is 5 parts by weight.

In another embodiment, component b comprises copper oxide and manganese dioxide. In this embodiment, the binder is preferably cohoidd dumina. In this embodiment, the acid is preferably acetic acid. In this embodiment, the binder is from 1 to 98 parts by weight, preferably from 5 to 35 parts by weight, the copper oxide is from 1 to 98 parts by weight, preferably from 35 to 55 parts by weight, and the manganese dioxide is from 1 to 98 parts by weight, preferably from 25 to 55 parts by weight. In another embodiment, the binder is 20 parts by weight, copper oxide is 40 parts by weight, and manganese dioxide is 40 parts by weight. In another embodiment, component b comprises duminum oxide, copper oxide, manganese dioxide and activated carbon. In this embodiment, the binder is preferably cohoidd dumina. In this embodiment, the acid is preferably acetic acid. In this embodiment, the binder is from 1 to 96 parts by weight, preferably from 5 to 35 parts by weight, the duminum oxide is from 1 to 96 parts by weight, preferably from 45 to 75 parts by weight, the copper oxide is from 1 to 96 parts by weight, preferably from 1 to 20 parts by weight, the manganese dioxide is from 1 to 96 parts by weight, preferably from 1 to 20 parts by weight, and activated carbon is from 1 to 96 parts by weight, preferably from 1 to 25 parts by weight. In another embodiment, the binder is 19.9 parts by weight, duminum oxide is 60 parts by weight, copper oxide is 5.98 parts by weight, manganese dioxide is 4.98 parts by weight, and activated carbon is 9.95 parts by weight.

In another embodiment, the component b comprises duminum oxide, silicon dioxide and activated carbon. In a further embodiment, the particle comprises from 1 to 97 parts, preferably 5-35 parts, more preferably 20 parts by weight duminum oxide, from 1 to 97 parts, preferably 5-35 parts, more preferably 20 parts by weight silicon dioxide and 1-99 parts, preferably 25-55 parts, more preferably 40 parts by weight activated carbon. In this embodiment, the binder is preferably cohoidd dumina and the acid is preferably acetic acid. The binder is from 1 to 97 parts by weight, preferably from 5 to 35 parts by weight.

In another embodiment, the catdyst and binder system can be used as an oxidation catdyst. In one embodiment, the system comprises cohoidd dumina as a binder, Al₂O₃, and one or more of the following oxide particles of N₂O₅, W0₂, WO₃, TiO₂, Re₂O₇, As₂O₃, As₂O₅, OsO₄, or Sb₂O₃ . In another embodiment, the cohoidd dumina is from 10 to 30 parts by weight, Al₂O₃ is from 1 to 90 parts by weight, and V₂O₅, W0₂, W0₃, TiO₂, Re₂0₇, As₂O₃, As₂O₅, OsO₄, or Sb₂O₃ are each from 1 to 90 parts by weight. In another embodiment, the catdyst and binder system can be used as a Lewis acid catdyst. In one embodiment, the system comprises cohoidd dumina as a binder, Al₂O₃, and one or more of the fohowing oxide particles of V₂O₅, Zr0₂, TiO₂, MgO, ThO₂ or lanthanide oxides. In another embodiment, the cohoidd dumina is from 10 to 30 parts by weight, Al₂O₃ is from 1 to 90 parts by weight, and V₂O₅, ZrO₂, TiO₂, MgO, ThO₂ or lanthanide oxides are each from 1 to 90 parts by weight.

In another embodiment, the catdyst and binder system can be used as a cracking catdyst. In one embodiment, the system comprises cohoidd dumina as a binder, Al₂O₃, and one or more of the fohowing oxide particles of CuO, ZnO, Ag₂O, AgO, CdO, Sn0₂, PbO, V₂O₅, ZrO₂, MgO, ThO₂ or lanthanide oxides. In another embodiment, the cohoidd dumina is from 10 to 30 parts by weight, Al₂O₃ is from 1 to 90 parts by weight, and CuO, ZnO, Ag₂O, AgO, CdO, SnO₂, PbO, N₂O₅, ZrO₂, MgO, ThO₂ or lanthanide oxides are each from 1 to 90 parts by weight.

In another embodiment, the catdyst and binder system can be used as a reduction catdyst. In one embodiment, the system comprises cohoidd dumina as a binder, Al₂O₃, and one or more of the fohowing oxide particles of MnO₂, Fe₂0₃, Fe^, RuA, OsO₄, CoO, Co₂0₃, RuO or ΝiO. In another embodiment, the cohoidd dumina is from 10 to 30 parts by weight, Al₂O₃ is from 1 to 90 parts by weight, and Mn0₂, Fe₂O₃, Fe₃O₄, u^, OsO₄, CoO, Co₂O₃, RuO or ΝiO are each from 1 to 90 parts by weight.

In one embodiment, the adsorbent and/or catdyst and binder system comprises a binder that has been cross-linked with at least one type of oxide adsorbent and/or catdyst particle, wherein (1) the binder comprises a cohoidd metd oxide or cohoidd metalloid oxide, preferably cohoidd silicon dioxide, cohoidd duminum oxide, or a combination thereof, and (2) the particle comprises duminum oxide, silicate, diatomaceous earth, or a combination thereof. In one embodiment, the binder is cohoidd duminum oxide and the particle comprises duminum oxide, silicate, and diatomaceous earth. In another embodiment, the binder is cohoidd duminum oxide and the particle comprises duminum oxide and diatomaceous earth. In another embodiment, the binder is cohoidd silicon dioxide and the particle comprises duminum oxide, s icate, and diatomaceous earth. In another embodiment, the binder is cohoidd duminum oxide and cohoidd silicon dioxide and the particle comprises silicate and diatomaceous earth.

In another embodiment, the catdyst and binder system can be used as a catdyst for the reduction and removd of nitrogen oxides. In one embodiment, the binder is cohoidd dumina and the particle comprises duminum oxide, gallium oxide and copper oxide. In another embodiment, the cohoidd dumina is from 1 to 98% by weight, the duminum oxide is from 1 to 98% by weight, the gallium oxide is from 1 to 98% by weight, and the copper oxide is from 1 to 99% by weight. In yet another embodiment, the cohoidd dumina is from 5 to 40% by weight, the duminum oxide is from 40 to 99% by weight, the gallium oxide is from 1 to 10% by weight, and the copper oxide is from 1 to 10% by weight. In a preferred embodiment, the cohoidd dumina is 20% by weight, A1₂0₃, preferably acid enhanced, is 70% by weight, Ga^ is 5% by weight, and CuO is 5% by weight, wherein the particle is cross-linked with acetic acid at 350°C. In another embodiment, the binder is cohoidd dumina and the particle comprises duminum oxide, copper oxide and zhconium oxide. In yet another embodiment, the cohoidd dumina is from 1 to 97% by weight, the duminum oxide is from is from 1 to 97% by weight, and the copper oxide is from 1 to 97% by weight, and the zirconium oxide is from 1 to 97% by weight. In a preferred embodiment, the cohoidd dumina is from 10 to 40% by weight, the duminum oxide is from 30 to 70% by weight, the copper oxide is from 10 to 20% by weight, and the zirconium oxide is from 1 to 20% by weight. In an even more preferred embodiment, the cohoidd dumina is 20% by weight, the Al₂O₃, preferably acid enhanced, is 70% by weight, CuO is 5% by weight, and ZrO₂ is 5% by weight, wherein the particle is cross-linked with acetic acid at 350 °C. In another embodiment, the binder is cohoidd dumina and the particle comprises duminum oxide and silver nitrate. In yet another embodiment, the cohoidd dumina is from 1 to 98% by weight, the duminum oxide is from is from 1 to 98% by weight, and the silver nitrate is from 1 to 98% by weight. In a preferred embodiment, the cohoidd dumina is from 10 to 40% by weight, the duminum oxide is from is from 30 to 70% by weight, and the silver nitrate is from 1 to 20% by weight. In a preferred embodiment, the cohoidd dumina is 20% by weight, Al₂O₃, preferably acid enhanced, is 75% by weight, and AgNO₃ is 5% by weight, wherein the particle is cross-linked with acetic acid at 350 °C. In another embodiment, the binder is cohoidd dumina and the particle comprises duminum oxide, a mixed oxide complex, and copper oxide.

Mixed oxides complexes are defined as particles comprising at least two or more oxide complexes. In yet another embodiment, the cohoidd dumina is from 1 to 97% by weight, the duminum oxide is from is from 1 to 97% by weight, the mixed oxide is from 1 to 97% by weight, and the copper oxide is from 1 to 97% by weight. In a preferred embodiment, the cohoidd dumina is from 10 to 40% by weight, the duminum oxide is from 30 to 70% by weight, the mixed oxide is from 1 to 20% by weight, and the copper oxide is from 1 to 20% by weight. A mixed oxide particle that is useful for this embodiment is MOLECULITE^®, which is by supphed Molecular Products LTD., Essex, UK. MOLECULITE^® contains from 60 to 75% by weight oxides of manganese compounds, including MnO₂, Mn₂O₃, and/or Mn₃O₄, 11 to 14% by weight copper oxide, and about 10% by weight htliium hydroxide. In one embodiment, the system comprises cohoidd dumina as a binder, and the particle comprises duminum oxide and copper oxide. In an even more preferred embodiment, the cohoidd dumina is 20% by weight, the ALOg, preferably acid enhanced, is 70% by weight, the MOLECULITE^® is 5% by weight, CuO is 5% by weight, wherein the particle is cross-linked with acetic acid at 350 °C. In another embodiment, the binder is cohoidd du ina and the particle comprises duminum oxide, copper oxide, manganese dioxide and magnesium oxide. In yet another embodiment, the cohoidd dumina is from 1 to 96% by weight, the duminum oxide is from is from 1 to 96% by weight, the manganese dioxide is from 1 to 96% by weight, the copper oxide is from 1 to 96% by weight, and the magnesium oxide is from 1 to 96%. In a preferred embodiment, the cohoidd dumina is from 10 to 40% by weight, the duminum. oxide is from is from 30 to 70% by weight, the manganese dioxide is from 1 to 20% by weight, the copper oxide is from 1 to 20% by weight, and the magnesium oxide is from 1 to 30%. In an even more preferred embodiment, the cohoidd dumina is 20% by weight, Al₂O₃, preferably acid enhanced, is 50% by weight, the MnO₂ is 5% by weight, CuO is 5% by weight, and MgO is 20%, wherein the particle is cross-linked with acetic acid at 350°C. In yet another embodiment, the cohoidd dumina is from 1 to 98% by weight, the duminum oxide is from is from 1 to 98% by weight, and the copper oxide is from 1 to 98% by weight. In a preferred embodiment, the cohoidd dumina is from 10 to 40% by weight, the duminum oxide is from 30 to 70% by weight, and the copper oxide is from 1 to 20% by weight. In an even more preferred embodiment, the cohoidd dumina is 25% by weight, Al₂O₃, preferably acid enhanced, is 65% by weight, and CuO is 10% by weight, wherein the particle is cross-linked with acetic acid at 350 °C.

In another embodiment, the catdyst and binder system can be used as a catdyst for oxidation of CO and hydrocarbons. In one embodiment, the binder is cohoidd dumina and the particle comprises duminum oxide, a mixed oxide and copper oxide. In yet another embodiment, the cohoidd dumina is from 1 to 98% by weight, the alvrminum oxide is from is from 1 to 98% by weight, and the mixed oxide is from 1 to 98% by weight. In a preferred embodiment, the cohoidd dumina is from 10 to 40% by weight, the duminum oxide is from 10 to 40% by weight, and the mixed oxide is from 20 to 70% by weight. A mixed metd oxide that is useful in this embodiment is CARULITE^® 300, which is supphed by Cams Chemicd Company, LaSahe, Illinois, USA. CARULITE^® 300 contains from 60 to 75% by weight manganese dioxide, 11 to 14% copper oxide, and 15 to 16% duminum oxide. In an even more preferred embodiment, the cohoidd dumina is 20% by weight, Al₂O₃, preferably acid enhanced, is 20% by weight, and CARULITE^® 300 is 60% by weight, wherein the particle is cross-linked with nitric acid at 350 °C.

In another embodiment, the catdyst and binder system can be used as an adsorbent for sulfur oxygen compounds. In one embodiment, the system comprises cohoidd dumina as a binder, and the particle comprises duminum oxide and copper oxide. In another embodiment, the cohoidd dumina is from 1 to 98% by weight, the duminum. oxide is from is from 1 to 98% by weight, and the copper oxide is from 1 to 98% by weight. In a preferred embodiment, the cohoidd dumiha is from 10 to 40% by weight, the duminum oxide is from is from 30 to 70% by weight, and the copper oxide is from 1 to 20% by weight.

In another embodiment, the binder and oxide adsorbent and/or catdyst system can remove chlorinated hydrocarbons from a hquid strea In one embodiment, the binder and oxide adsorbent and/or catdyst system comprises (1) cohoidd du ina, (2) duminum oxide, (3) a mixed oxide, such as mixed oxides of manganese, for example MOLECULITE^®, and (4) carbon. In a preferred embodiment, the composition comprises or consists of cohoidd dumina from 10 to 30, preferably 20% by weight, A1₂0₃ , which is preferably acid enhanced, from 50 to 70, preferably 60% by weight, MOLECULITE^® from 5 to 15, preferably 10% by weight, and carbon from 5 to 15, preferably 10% by weight.

In another embodiment, the catdyst and binder system can be used as a cod gasification catdyst. In one embodiment, the system comprises cohoidd dumina as a binder, Al₂O₃, and one or more of the fohowing oxide particles of Fe₂O₃, Fe₃O₄, CoO or Co₂O₃. In another embodiment, the cohoidd dumina is from 10 to 30 parts by weight, Al₂O₃ is from 1 to 90 parts by weight, and Fe₂O₃, Fe_jO₄, CoO, or Co₂O₃, are each from 1 to 90 parts by weight. In another embodiment, the catdyst and binder system can be used as a cod gas reforming catdyst. In one embodiment, the system comprises cohoidd dumina as a binder, Al₂O₃, and one or more of the fohowing oxide particles of Fe₂O₃, Fe₃O₄, CoO or Co₂O₃. In another embodiment, the cohoidd dumina is from 10 to 30 parts by weight, A1₂0₃ is from 1 to 90 parts by weight, and Fe₂O₃, Fe₃O₄, CoO, or Co₂O₃, are each from 1 to 90 parts by weight.

In another embodiment, the catdyst and binder system can be used as a hydrogenation catdyst. In one embodiment, the system comprises cohoidd dumina as a binder, A1₂0₃, and one or more of the fohowing oxide particles of Fe₂O₃, Fe₃O₄, CoO or Co₂O₃. In another embodiment, the cohoidd dumina is from 10 to 30 parts by weight, A1₂0₃ is from 1 to 90 parts by weight, and Fe₂0₃, Fe₃O₄, CoO or Co₂O₃ are each from 1 to 90 parts by weight.

In another embodiment, the catdyst and binder system can be used as a desiccant. In one embodiment, the system comprises cohoidd dumina as a binder, Al₂O₃, and one or more of the fohowing oxide of zeohte, MgO, or ThO₂. In another embodiment, the cohoidd dumina is from 10 to 30 parts by weight, Al₂O₃ is from 1 to 90 parts by weight, and zeohte, MgO, or ThO₂ are each from 1 to 90 parts by weight.

In another embodiment, the catdyst and binder system can be used as a catdyst support. In one embodiment, the system comprises cohoidd dumina as a binder, Al₂O₃, and one or more of the fohowing oxide particles of MgO or ThO₂. In another embodiment, the cohoidd dumina is from 10 to 30 parts by weight, Al₂O₃ is from 1 to 90 parts by weight, and MgO or ThO₂ are each from 1 to 90 parts by weight.

In another embodiment, the catdyst and binder system can be used to adsorb ions from a gas or hquid stream. In one embodiment, the system comprises cohoidd dumina as a binder, duminum oxide and copper oxide. In yet another embodiment, the cohoidd dumina is from 1 to 98% by weight, the duminum oxide is from is from 1 to 98% by weight, and the copper oxide is from 1 to 98% by weight. In a preferred embodiment, the cohoidd dumina is from 10 to 40% by weight, the duminum oxide is from is from 30 to 70% by weight, and the copper oxide is from 1 to 20% by weight. The ion that is adsorbed includes but is not limited to an anion, an oxo-anion, a poly- oxoanion or a mixture thereof.

In another embodiment, the system comprises colloidd dumina binder and the particle comprises duminum oxide, zinc oxide and copper oxide. In another embodiment the system comprises a cohoidd dumina binder and the particle comprises duminum. oxide and copper oxide.

In another embodiment, the catdyst and binder system can encapsulate a contaminant within an adsorbent particle. The acid enhanced adsorbent and/or catdyst particle of section I above and the binder and oxide adsorbent and/or oxide particle of this section II may be used to encapsulate a contaminant. Upon heating h e adsorbent particle that has adsorbed a contaminant to a sufficient temperature, the pores of the particle will close and encapsulate the contaminant within the particle. In one embodiment, the curing temperature is from 450°C to 1200°C, preferably from 600°C to 1200°C. Upon heating the particle or the binder-particle system, the pores of the particle, binder or both will close and encapsulate the contaminant.

The acid that is used to enhance the particle of section I above and the acid used to cross-link the binder and oxide adsorbent and/or catdyst particle of this section can dso behave as a blowing agent. The term blowing agent is defined herein as any reagent that can modify a physicd property of the particle. Examples of physicd properties that can be modified include but are not limited to surface area, pore area, bulk density, skeletd density and porosity. In one embodiment, the blowing agent can be an acid, preferably a low molecular weight carboxylic acid, preferably acetic and formic acid. Not to be bound by theory, it is beheved that the acid can bind with the particle of section I during acid treatment or enhancement or the acid can bind to the binder and/or oxide adsorbent and/or catdyst system of this section during the mixing, kneading and extrusion steps. The complex then decomposes during the curing step to produce gasses. The resultant gas departs from the particle, which resdts in an increase in surface area, pore area bulk density, skeletd density and porosity. By varying the physicd properties of the particle, the activity of the adsorbent and/or activity of the catdyst can be enhanced.

In another embodiment, the invention relates to a composition for binding adsorbent and/or catdytic particles to produce an agglomerated particle comprising (a) a cohoidd metd oxide or cohoidd metahoid oxide and (b) an acid. In this composition, in one embodiment, the cohoidd metd oxide or cohoidd metahoid oxide comprises cohoidd dumina or cohoidd sihca. In this composition, in one embodiment, the acid is acetic acid or nitric acid.

In another embodiment, the invention relates to a method for binding adsorbent and/or catdytic particles, comprising the steps of:

(a) mixing cohoidd dumina or cohoidd sihca with the particles and an acid;

(b) agitating the mixture to homogeneity; and

(c) heating the mixture for a sufficient time to cause cross-linking of the duminum oxide in the mixture.

In one embodiment, the cohoidd dumina or cohoidd sihca is cohoidd dumina. In another embodiment, the cohoidd dumina is from 20% to 99% by weight of the mixture. In another embodiment, the acid is nitric acid.

III. ANCHORED ADSORBENT AND/OR CATALYST SYSTEM The use of organic and inorganic materids as catdyst and/or adsorbent systems is known in the art. These catdyst support systems are capable of binding with a homogeneous catdyst. A homogeneous catdyst is defined as a catdyst that is in the same phase as the reactants. There are two main advantages to using a catdyst support system in combination with a homogeneous catdyst. First, the homogeneous catdyst that is bound or complexed to the support is recoverable after the reaction is complete. A number of homogeneous catdysts that are used in the art are expensive to manufacture; therefore, the recovery of these materids is important. Second, the support can enhance the activity of the anchored homogeneous catdyst. An anchored catdyst is defined as a catalyst that is bound to a support system

The complexation of a catdyst to an inert support, for example, a polymer such as polystyrene has been the focus of extensive research in the prior art. The use of metd oxides as catdyst supports have dso been used extensively in catdytic reactions. A review of anchored catdysts systems is disclosed in Ndentine et al. , "Technologicd Perspective for Anchored Catdysts Preparation," Am. Che Soc, Div. Pet. Chem, Vol. 27(3), pp. 608-10, 1982; Pittman et al "Unusud Selectivities in Hydroformylations Catdyzed by Polymer- Attached Carbony ydrotris(triphenylphosplime)rhodium," J. A Chem. Soc. Nol 98(17), pp 5402-5, 1976; Jacobson et al. , "Selective Hydrogenation of 4-Ninylcyclohexene Catdyzed by Polymer- Anchored CarbonylcHorobis(triphenylphospllme)mdium,^,, J. Mol. Catd. Nol. 1(1), pp 73-6, 1975; Pittman et al. "The Vinyl Reactivity of (5-Vmylcyclopentadienyl)dicarbony trosylclιromium. A Novel Vinyl Organometahic Monomer", Macromolecules Vol. 11, pp 560-565, 1978; and Cotton et al. "Advanced Inorganic Chemistry; A Comprehensive Text," 3rd edition, pp 620-801, 1962.

Although a number of support systems are known in the art, they are limited in that current polymer supports systems are hrnited to reaction conditions where the polymer is stable. The prior art support systems are composed of an organic polymer backbone, or a single component metd oxide syste

In one embodiment, the invention relates to an adsorbent and/or catdyst and binder system, comprising:

(a) a pendant hgand substituted or unsubstituted binder, and

(b) a pendant hgand substituted or unsusbtituted oxide adsorbent and/or oxide catdyst particle, wherein at least one of components (a) and (b) is pendant hgand substituted, and wherein component (a) is cross-linked with component (b).

The unsubstituted binder and unsusbstituted oxide adsorbent and/or oxide catdyst particle is defined herein as a particle that has free hydroxyl groups that have not been substituted with an organic or inorganic pendant hgand moiety. The binder and oxide adsorbent and/or oxide catdyst particles and system discussed in the previous section entitled "Binder and Oxide Adsorbent and/or Oxide Catdyst System" can be used as the unsubstituted binder and unsubstituted oxide adsorbent and/or oxide catdyst particles and systems.

In one embodiment, the binder can be a cohoidd metd oxide or a cohoidd metahoid oxide, preferably cohoidd dumina, cohoidd sihca, a cohoidd metd oxide wherein the metd is iron, or a mixture thereof, and even more preferably cohoidd dumina, cohoidd sihca, or a mixture thereof, and even more preferably cohoidd dumina as defined above in section II.

In one embodiment, the oxide adsorbent and/or oxide catdyst particle is pendant hgand substituted. In another embodiment, the binder is pendant hgand substituted. In an another embodiment, the oxide adsorbent and/or oxide catdyst particle and the binder are both pendant hgand substituted. The substituted binder and oxide adsorbent and/or oxide catdyst system independently contains at least one pendant hgand. In one embodiment, a pendant hgand is defined herein as a moiety having at least one complexing group and, optionally, a tether end. The complexing group is typicahy the moiety of the pendant hgand used to attach or bind to a metd complex, wherein the metd complex can be a homogeneous catdyst that is known in the art and are disclosed, for example, in Cohman et al, "Principles and Apphcations of Organo transition Metd Chemistry," Ch. 2, 1987, can be used herein. In one embodiment, the complexing group is a group with a lone-pair of electrons. In this case, the complexing group can bind to another moiety by way of a Lewis acid-base interaction. Examples of groups that possess lone-pairs of electrons and can behave as complexing agents include but are not limited to a hydroxyl group, an ether, a thiol, a thio ether, an amine, a mono- or disubstituted amine, a phosphine, a mono- or disubstituted phosphine or a mixture thereof. Typicahy, the pendant hgand has a tether group (or "tether end"), but herein there are embodiments wherein the complexing group can directly bond to the binder/oxide adsorbent and/or catdyst system without a tether.

In another embodiment, the complexing group can be an unsaturated organic moiety. The unsaturated organic moiety can be but is not limited to a cychc, acychc or aromatic moiety. In one embodiment, the acychc unsaturated organic moiety can include but is not limited to an olefin, an ahyl, a diene, a triene, an alkene, or a mixture thereof. In yet another embodiment, the acychc unsaturated organic moiety has the formula -(CH=CH)_nCH=CH₂, wherein n is from 1 to 5, preferably from 1 to 3.

In another embodiment, the complexing group can be a cychc unsaturated organic moiety. Examples of cychc unsaturated organic moieties include but are not limited to cyclopentadiene, cycloheptatriene, cyclooctadiene, cyclooctetraene, or the corresponding anion thereof, or a mixture thereof. In another embodiment, the complexing agent can be an aromatic unsaturated organic moiety. Examples of aromatic unsaturated organic moieties include but are not hmited to benzene, naphthdene, anthracene or mixtures thereof.

The pendant hgand moiety can dso have a tether end. The tether end connects the complexing group end of the hgand to the binder or oxide adsorbent and/or oxide catdyst particle. If no tether is present, the complexing group is directly attached to the binder or oxide adsorbent and/or oxide catdyst particle. The tether end can comprise an aliphatic group, an aromatic group, a silyl group, a siloxy group or a combination thereof or an ohgomer or polymer thereof. The length of the tether end can vary depending upon the end-use. In one embodiment, the tether end can be an aliphatic or aromatic group that is from 1 to 30 carbons, preferably from 1 to 10 carbons, and even more preferably from 1 to 5 carbons. The tether end can be branched or unbranched and substituted or unsubstituted. In another embodiment, the tether end can be a shane, a polysiloxane, a mixed hydrocarbon-silane, a hydrocarbon-siloxane, or a mixture thereof.

In another embodiment, the invention relates to an anchored adsorbent and/or catdyst and binder system, comprising: (a) a pendant hgand substituted or unsubstituted binder, and

(b) a pendant hgand substituted or unsusbtituted oxide adsorbent and/or oxide catdyst particle, and

(c) a metd complex, wherein at least one of components (a) and (b) is pendant hgand substituted, wherein component (a) is cross-linked with component (b), and wherein the metd complex (c) is bound to component (a) and/or (b).

The pendant hgand substituted binder and oxide adsorbent and/or catdyst system described above can be incorporated with a metd complex. As discussed above, in one embodiment, the pendant hgand possesses a complexing group which can bind to a metd complex (c). Examples of metd complexes that can be bound to the substituted binder and/or catdyst system include but are not limited to a metd sdt, metd carbonyl complex, metd phosphine complex, metd amine complex, a metd hydride complex, a metd olefin complex, a metd acetylene complex, a metd polyene complex, a metd halide complex or a mixture thereof. In one embodiment, the metds that can be used in metd carbonyl complexes, metd phosphine complexes, metd amine complexes, metd olefin complexes, metd acetylene complexes, metd polyene complexes, and metd halide complexes include the transition, lanthanide and actinide metals.

In one embodiment, the metd sdt can be a halide, a carbonate, an oxdate, a bicarbonate, or a carboxylate as the counterion and hthium, sodium, potassium, rubidium, cesium, francium, magnesium, cdcium, strontium, barium, radon, the transition metds, the lanthanide metds or the actinide metds as the metd moiety.

In another embodiment, the metd carbonyl can be a mono-nuclear or poly- nuclear binary carbonyl of a transition metd. Examples of metd carbonyls useful in the present invention include but are not hmited a mono-nuclear or poly-nuclear mixed carbonyl-phosphine, carbonyl-phosphite, carbonyl-olefin, carbonyl- acetylene, carbonyl- cyclopentadienyl complexes, carbonyl-hydride, or carbonyl-hahde of a transition metd.

The substituted binder and oxide adsorbent and/or catdyst system can be used as a support system and bind to a metd complex, which acts as a second catalyst. In one embodiment, the second catdyst can be a homogeneous catdyst. A number of homogeneous catdysts are known in the art and are disclosed in Parshah, "Homogeneous Catdysis," 1980. Examples of homogeneous catdysts that can be anchored to the substituted binder and oxide adsorbent and/or catdyst system include but are not limited to a hydrogenation catdyst, an oxidation catdyst, a hydroformylation catdyst, a reduction catdyst, an isomerization catdyst, a polymerization, a carbonylation catdyst, a reforming catdyst, an olefin metathesis catdyst, a Fischer-Tropsch catdyst, a gasification catdyst or a mixture thereof.

In another embodiment, the invention relates to a method for producing a pendant hgand substituted adsorbent and/or catdyst system, comprising: (i) mixing components, comprising:

(a) a pendant hgand substituted or unsubstituted binder comprising a cohoidd metd oxide or a cohoidd metalloid oxide, (b) a pendant hgand substituted or unsubstituted oxide adsorbent and/or oxide catdyst particle, and (c) an acid, wherein at least one of components (a) and (b) is pendant hgand substituted, and (ii) removing a sufficient amount of water from the mixture to cross-link components (a) and (b) to form a pendant hgand substituted adsorbent and/or catdyst and binder system.

The method further comprises( i) binding a metd complex onto the resulting system of step (ii) to form the anchored catdyst system

The unsubstituted binder and unsubstituted oxide adsorbent and/or oxide catdyst particles of the present invention can be converted to the pendant hgand substituted andogs using techniques weh known in the art and are disclosed in Eisen et al. , "Catdytic Activity of Some Iriimobihzed Dirhodium Complexes with One Bridging Thiolato and One Bridging Chloro Ligand" J. Mol. Catd. Vol. 43(2), pp 199-212, 1987; Cermak et al, "Hydrogenation Catdytic Activity of Substituted Cyclopentadienyl Titanium Complexes Anchored on Polysiloxanes Prepared by a Sol-Gel Procedure," J. Organomet. Chem Vol. 509(1), pp 77-84, 1996; Doi et al. "Metd Cluster Catdysis: Preparation and Catdytic Properties of Anionic Triruthenium Clusters Anchored to Functionahzed Sihca," Inorg. Chim. Acta, Vol 105(1), pp 69-73, 1985; Doi et al. "Metd Cluster Catdysis: Preparation and Catdytic Properties of a Tetrarathenium Cluster Anchored to Sihca via Phosphine Ligands," J. Mol. Catd., Vol 19(3), pp 359-63, 1983, which are hereby incorporated by these references.

The reaction between the unsubstituted 1) binder and/or 2) oxide adsorbent and/or oxide catdyst particle and a hydroxyl-reactive compound produces the substituted binder and oxide adsorbent and/or oxide catdyst particle. In one embodiment, the unsubstituted binder reacts with a hydroxyl-reactive compound to produce a pendant hgand substituted binder. In another embodiment, the unsubstituted oxide adsorbent and/or oxide catdyst particle reacts with a hydroxyl-reactive compound to produce a pendant hgand substituted oxide adsorbent and/or oxide catdyst particle. In another embodiment, the unsubstituted binder and an unsubstituted oxide adsorbent and/or oxide catdyst particle react with a hydroxyl-reactive compound to produce a pendant hgand substituted binder and a pendant hgand substituted oxide adsorbent and/or oxide catdyst particle. The pendant hgand substituted binder and a pendant hgand substituted oxide adsorbent and/or oxide catdyst particle may have free hydroxyl groups that have not been substituted with the pendant hgand. Once the substituted binder and/or oxide adsorbent and/or catdyst particle have been prepared, they can be combined using the techniques described above for preparing the binder and oxide adsorbent and/or catdyst system.

The hydroxyl-reactive compound is any compound that is capable of reacting with the free hydroxyl groups of the unsubstituted binder and oxide adsorbent and/or oxide catdyst particle. The hydroxyl-reactive compound dso possesses a complexing group and can have a tether end as described above. In one embodiment, the hydroxyl- reactive compound can be an aJkylating agent, an dcohol, a carboxylic acid, an organic ester, an organic anhydride, an organic tosylate, a trialkyloxonium cation, a shane, a silyl halide, a siloxy compound, an organic acid halide, an organic orthformate, phosphine, mono- or di-substituted phosphine, phosphine trihahde, mono- or disubstituted phosphine halide, phosphorus pentahahde, phosphorus oxo halide, phosphonates, phosphates, phosphites, or condensed phosphates and their derivatives. . In a preferred embodiment, the hydroxyl-reactive compound is an alkylating agent. In an even more preferred embodiment, the alkylating agent is an aliphatic or arahphatic halide. In one embodiment, the aliphatic or arahphatic group can be from 1 to 20 carbons, preferably from 1 to 10 carbons, and even more preferably from 1 to 5 carbons. The ahphatic and arahphatic groups can be branched or unbranched and substituted or unsubstituted. In another embodiment, a silylating agent can be used. Silylating agents useful in the present invention include but are not hmited to alkyl and aryl silyl halides. In another embodiment, the silylating agent can be a shane, a polysiloxane, a mixed hydrocarbon-silane, a hydro carbon- siloxane, or a mixture thereof.

Once the substituted binder and oxide adsorbent and/or catdyst system has been prepared, a metd complex can be bound, such as complexing, coordinating, chelating, bonding, to the resulting syste Techniques for incorporating or binding the metd complex in the support are disclosed in Gates, "Catdytic Materids," Chapter 12, pp 301-320, in "Materids Chemistry; An Emerging Discipline," Edited by Interrante, L. V.; Casper et al. in "Advances in Chemistry Series 245, American Chemicd Society, Washington, D.C. 1995, which are hereby incorporated by these references. Examples of techniques used to incorporate the metd complex onto the support include but are not limited to vapor deposition, incipient wetness, aqueous impregnation or non- aqueous impregnation.

In another embodiment, the invention relates to an adsorbent and/or catdyst and binder system, comprising: (a) a pendant hgand substituted or unsubstituted binder, and

(b) a pendant hgand substituted or unsusbtituted oxide adsorbent and/or oxide catdyst particle,

wherein at least one of components (a) and (b) is pendant hgand substituted, wherein component (a) is cross-linked with component (b), and wherein the pendant hgand has at least one chird center.

In a further embodiment, the invention relates to an anchored adsorbent and/or catdyst and binder system, comprising:

(a) a pendant hgand substituted or unsubstituted binder;

(c) a metd complex,

wherein at least one of components (a)-(c) is a chird pendant hgand substituted, wherein component (a) is cross-linked with component (b), and wherein the metd complex (c) is bound to component (a) and/or (b).

The use of chird hgands in homogeneous and heterogeneous catdysis and chromatography is weh known in the art. A chird center is an atom or group of atoms that is nonsuperimposϊble upon its mirror image. The chird center is an atom that has four different groups attached to it. One group that can be attached to the chird center is a lone pair of electrons. In one embodiment, the chird hgand has one or more chird centers and one or more lone pair electrons. When the chird hgand has one or more lone pair electrons, it can coordinate with a Lewis base. The chird hgands disclosed in "Asymmetric Synthesis, Volume 4; The Chird Carbon Pool, and Chird Sulfur, Nitrogen, Phosphorus, and Silicon Centers" Edited by James, D. Morrison and John W. Scott, Academic Press, Inc., 1984, and "Asymmetric Synthesis, Volume 5; Chird Catdysis" Edited by James, D. Morrison, Academic Press, Inc., 1985, which are incorporated by reference in their entireties, can be used in the present invention. Examples of chird hgands useful in the present invention include, but are not limited to, phosphines and amines. In one embodiment, the pendant hgand comprises one or more chird carbon, sulfur, nitrogen, phosphorous, or silicon centers, or a combination thereof.

In one embodiment, the pendant hgand substituted binder is represented by the generd formula Binder XRR', where denotes any of the tethers described above, X is nitrogen or phosphorous, and R and R' are, independently, alkyl, aryl, cycloalkyl, aralkyl, heteroaryl, alkenyl, or alkynyl, where R and R' are not the same. In another embodiment, the pendant hgand substituted binder is represented by the generd formula Binder PR^H^PR'R", where denotes any of the tethers described above, and R, R' , and R" are, independently, alkyl, aryl, cycloalkyl, aralkyl, heteroaryl, alkenyl, or alkynyl, where R and R' are not the same. In this embodiment, the chird hgand has two chird centers.

In another embodiment, the chird pendant hgand can be an amino acid. The amino acid can be any naturd or non-naturd amino acid. In one embodiment, the amino acid can be directly attached to the binder and/or adsorbent and/or oxide particle by the COOH group of the amino acid to produce the corresponding ester of the amino acid. For example, the binder of the present invention possesses surface hydroxyl groups that can react with the carboxylic acid group of the amino acid to produce the corresponding ester. In another embodiment, amino acid can be bound to the binder and/or adsorbent and/or oxide particle through the nitrogen of the amino group of the -imino acid. In one embodiment, any of the tethers described above can be used to attach the amino acid to the binder and/or adsorbent and/or oxide paiticle through the amino nitrogen.

In one embodiment, an adsorbent and/or catdyst and binder system containing at least one chird center can be used in chromatography. Chromatography is a technique well-known in the art, and is used to separate a compound or compounds from a mixture of compounds. The phrase "pendant hgand" as used in this embodiment is defined herein as an organic group covdently bonded to the binder, metd oxide, or coparticle prepared therefrom. Such hgands that come into contact with a mixture of compounds can selectively adsorb particular certain compounds over others present in the mixture. This selective adsorption can be utilized to separate organic or inorganic compounds or mixtures of compounds. In one embodiment, the mixture of compounds comprises chird compounds which can be separated into mdividud enantiomers or diasteroisomers. In another embodiment, when the mixture is a racemic mixture, each enantiomer can be separated.

In another embodiment, the invention relates to a method for producing an adsorbent and/or catdyst and binder system comprising i) mixing components comprising a) a binder comprising a cohoidd metd oxide or cohoidd metahoid oxide, b) an oxide adsorbent and or oxide catdyst particle, and c) an acid, ii) removing a sufficient amount of water from the mixture to cross-link components a and b to form an adsorbent and/or catdyst and binder system, hi) reacting the resultant adsorbent and/or catdyst and binder system of step (ii) with a hydroxyl-reactive compound to form a pendant hgand substituted oxide adsorbent and/or oxide catdyst and binder syste

Treatment of the unsubstituted binder and oxide adsorbent and/or catdyst system with the hydroxyl-reactive compound produces the pendant hgand substituted binder and oxide adsorbent and/or catdyst system. In one embodiment, the unsubstituted binder reacts with a hydroxyl-reactive compound to produce a pendant hgand substituted binder. In another embodiment, the unsubstituted oxide adsorbent and/or oxide catdyst particle reacts with a hydroxyl-reactive compound to produce a pendant hgand substituted oxide adsorbent and/or oxide catdyst particle. In another embodiment, the unsubstituted binder and an unsubstituted oxide adsorbent and/or oxide catdyst particle react with a hydroxyl-reactive compound to produce a pendant hgand substituted binder and a substituted oxide adsorbent and/or oxide catdyst particle.

Once the pendant hgand substituted binder and oxide adsorbent and/or catdyst system has been prepared, a metd complex can be incorporated or bound onto the support using the techniques described above to produce an anchored catdyst system

In another aspect, the invention relates to an anchored adsorbent and/or catdyst and binder system, comprising:

(a) a binder, and

(b) an oxide adsorbent and/or oxide catdyst particle, and

(c) a metd complex, wherein at least one of components (a) and (b) is pendant hgand substituted, wherein component (a) is cross-linked with component (b), and wherein the metd complex (c) is bound directly to component (a) and/or (b).

In still yet another aspect, the invention relates to a method for producing an anchored adsorbent and/or catdyst system, comprising: (i) mixing components, comprising:

(a) a binder comprising a cohoidd metd oxide or a cohoidd metahoid oxide,

(b) an oxide adsorbent and/or oxide catdyst particle, and (c) an acid,

(ii) removing a sufficient amount of water from the mixture to cross-link components (a) and (b) to form a pendant hgand substituted adsorbent and/or catdyst and binder system, and

(hi) binding a metd complex directly onto the resulting system of step (ii) to form the anchored catdyst system.

In this embodiment of direct binding, the metd complex is bound directly to the (1) binder and/or (2) the oxide adsorbent and/or catdyst particle. The hydroxyl groups on the binder and the particle can behave as a complexing group as described above and can directly bind a metd complexes.

Any of the methods described above for producing an adsorbent and/or catdyst and binder system can use any of the chird pendant hgands described above.

EXPERIMENTAL

The fohowing examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds claimed herein are made and evduated, and are intended to be purely exemplary of the invention and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, and % is in weight %, temperature is in °C or is at room temperature and pressure is at or near atmospheric.

Example 1

Enhanced duminum oxide was made by the process of this invention using the fohowing steps:

i) Gamma duminum oxide particles were produced by cdcining Al(OH)₃ at a temperature of 550-560°C to produce cdcined Al₂O₃ of the gamma form.

ii) 20 hters of this duminum oxide were submerged in a tank containing 0.5% by weight acetic acid in distilled water. The totd volume of solution was 98.7 hters. The dumina was allowed to sit in the acid solution for approximately 15 minutes to allow saturation of the solution. The acid solution was drained off and the remaining dumina was rinsed in a tank of 30 hters of distilled water. The distilled water was drained and the remdning dumina was dried at a temperature of 121 °C for 90 minutes.

The performance of enhanced duminum oxide particles of this invention was tested. Two chromatographic columns, each 25 cm. long and 1 c inner diameter, equipped with a solvent reservoir were used for this experiment. Each column was packed with 20 cc of the above produced enhanced duminum oxide particles. Each column was flushed with 100 ml of water using pressure from the nitrogen cylinder to obtain a flow rate of approximately 20 ml per minute. A test solution of approximately 200 ppb of lead was prepared using lead acetate trihydrate. A totd of 200 ml (10 bed volumes) of test solution was passed through each column using the same flow rate. The influent, the totd effluent from the 10 bed volumes, and the effluent sample cohected during the tenth bed volume were andyzed for lead, and the results are summarized in Table 1.

Lower limit of lead detection was 5 μgm/hter.

This particle was dso tested using the TCLP method (EPA method # 6010), and the particle of the invention passed the TCLP test for lead.

Example 2

A comparison was made between acid enhanced dumina of this invention and non-acid-treated dumina for removing lead. Both duminum oxide particles were cdcined at 550 °C prior to the experiment. Enlianced gamma duminum oxide particles of the present invention were made according to the procedures of Example 1. Two identicd five gallon containers were filled with the dumina oxide for lead removd. One container was filled with 16 hters of the treated dumina of this invention. The other was filled with 16 hters of untreated dumina. Two tanks were prepared each containing 100 gahons of lead acetate tri-hydrate spiked disthled water. The tanks were mixed thoroughly for 30 minutes. After 30 minutes of mixing, the concentrations of the lead in the water were determined. The lead containing water from each tank was passed through the containers of dumina a totd of 80 gahons of spiked water (19 bed volumes) were passed through each of the containers at a flow rate of 62 gahons per minute. An effluent water sample was taken on the 19th bed volume and was andyzed for totd lead. The percent reductions were then cdculated. The results of the tests are set forth in Table 2 below.

Example 3

a comparison was made between treated dumina of this invention and non- treated dumina for removing phosphate. Chi-rho duminum oxide particles were produced by cdcining Al(OH)₃ at a particle temperature of 480-520 °C. Enhanced chi- rho duminum oxide particles of the present invention were acid treated according to the procedure of step (ii) in Example 1. The performance of the particles was measured using the same procedures of Example 1, except that one chromato graphic column was filled with 20 cc of the treated dumina and the other column was filled with 20 cc of the untreated dumina and the test solution was 9.3 mg 1 of KH₂P0₄, and the results are summarized in Table 3.

This particle of this invention from the experiment was dso tested using the TCLP method (EPA method # 1311), and the particle of the invention passed the TCLP test for phosphate.

Example 4

The ability of the particle of this invention to remove selenium was tested. Acid enhanced g-nrima dummum oxide particles (100% Al₂O₃) were made by the procedure of Example 1.

5 columns were prepared using 0.875" I.D. x 12" long glass columns, each with a bed volume of ~95 mis of the above acid enhanced Al₂O₃ particles of this invention of various particle sizes, ranging from 500 μm to 4,000 μm. Each bed was flushed with ~5 bed volumes of D.I. water by downward pumping at 5-6 gpm/ft cross sectiond flow rate (ie., ~95 mVmin). a test solution was prepared with a cdculated 1.5 mg/L selenium concentration, a totd of ~ 10 bed volumes (i e. , ~ 1 L per column) test solution was pumped through each column using the same flow rate. During the test, the test solution was continuously stirred at a low speed. During the tenth bed volume, an effluent sample from each column was cohected and andyzed for selenium. Also a single influent sample was cohected and andyzed for selenium. The results are set forth below.

a Selenium detection limit was 0.002 mg/1 Estimated vdue, less than calibration limit

Example 5

a combination particle of this invention was made and tested for its ability to remove trichloroethylene (TCE). 70 g of acid enhanced gamma duminum oxide particles made by the procedure of Example 1 were mixed with 20 g of cohoidd du ina, 5 g of MnO₂, and 5 g of CuO until the mixture was homogeneous. The particle mixture was then mixed with 5% acetic acid solution until the mixture reached a suitable consistency for agglomeration. The mixture was extruded and cut into a particle size of about 1,000 μm and heated to 150 °C for 15 minutes to crosslink the cohoidd dumina.

The particle as formed above was tested for its ability to remove TCE from water. Particles of the invention were chahenged with various concentrations of TCE in water as indicated in Table 1. Two custom made columns (40 cmX 20 mm) equipped with coarse glass frits were dried packed with 10 mL volumes (measured with a 10 mL graduated cylinder) of particles. The columns were chahenged with five 10 mL aliquots (5 bed volumes) of the TCE solution. The fifth bed volume from each column was cohected in a 50 mL Erlenmeyer flask, stoppered, and immediately andyzed by purge and trap-GC/MS technique using a Finnigan MAT Magnum ion trap GC/MS equipped with a Tekmar hquid sample concentrator (LSC 2000). The results are summarized in Table 5.

Example 6

TCE adsorption and TCLP extraction procedures were performed as fohows. a 20.0114-gram (about 24.50 mL bed volume) sample of the Al₂O₃/CuO/MnO₂ combination particle of Example 5 (designated as 0307595TCE1) after treatment with TCE was wet packed into a 50-mL buret (with removable stopcock) plugged with glass wool. The sample was charged with five bed volumes of water. The sorbent materid was then quantitatively transferred into the Zero Headspace Extractor (ZHE) apparatus into which 200 mL of water was added, appropriately seded and agitated for 18 hours. The filtered solution was cohected in two 100 mL vids, stored in the refrigerator at 4°C unth andysis by GC/MS. The Finnigan MAT Magnum ion trap GC/MS equipped with a Tekmar hquid sample concentrator (LSC 2000) was used for andysis.

The calibration curve procedure was as fohows. a freshly prepared 50 ppm TCE stock solution was obtained by dissolving 34.2 μl spectrophotometric grade TCE (Aldrich) in 20 ml HPLC grade methanol (Fisher) fohowed by dilution to a liter. Dilution of this solution (1000 μl : IL) resulted in a 50 ppb TCE stock solution. Ah dilutions were accomplished using deionized water, a calibration curve was constructed by purging 1.0, 0.50, 0.20, 0.10, and 0.050 ppb TCE solutions.

The results are set forth below.

Not detected. The fact that TCE in the sample is less that 500 ppb (EPA TCLP limit) characterizes it as a nonhazardous waste with respect to TCE.

Example 7

a 100 ml. portion of 1000 ppm phosphorous (potassium hydrogen phosphate and water) standard (Lab Chem, Inc.) was dhuted to 2 htres. Aliquots (200 ml) of the resulting stock solution containing 50 ppm phosphorous were tumbled for 24 h with duphcate approximately 2 ml (dry) volumes (both volumes and mass measured) of each dumina sample, and centrifuged. Acid enhanced ga ma dumina oxide particles of samples Pblk (CU), and Polk (CT) and acid enhanced chi-rho dumina oxide particles Pbhk (AU) and Pohk (At) were made by procedures of Example 1 except that the starting dumina "type" is different as shown in Table 7, and that the cdcining temperatures were different for the four samples as shown in Table 7 below. These materids were chahenged to determine the capacity of the dumina to remove phosphate (PO₄ ^"3) given the variables in starting materids and treatment. Ahquots (0.4 ml) of the supernatant were dhuted to 20 ml. To each of these solutions was added, with shaking, 2 drops phenolphthdein (Fisher), fohowed by 1 ml of ammonium molybdate reagent I and then 2 stops of stannous chloride reagent I (LabChem Inc.). Deteimination of aqueous phosphate was achieved by the measurement of color, photometricahy at 690 nm (path length, 0.5 cm) in a quartz ceh and read in a Shimadzu UV-2101PC, UV/VIS scanning spectrophotometer. AU dhutions were accomphshed using deionized water. The results are set forth below.

Example 8

Acid enlianced gamma dumina oxide particles of samples Pbhk (AU), Pohk (At), Pblk(CU), and Polk(CU) were made by procedures of Example 7. These materids were chahenged to determine the capacity of the dumina to remove lead (Fb^"1-1") given the variables in starting materids and treatment. A 500 ml portion of 400ppmof lead (0.6392 g Pb(NO₃)₂ dissolved in 10ml concentrated nitric acid and dhuted to one hter with deionized water) was dhuted to two hters with deionized water. Ahquots (450ml) of the resulting stock solution containing 50 ppm Pb, were tumbled for 24h with approximately 2ml (dry) volumes (both volume and mass measured) of each dumina sample, centrifuged, and stored prior to GFAA andysis. The instrument used was a Shimadzu AA-6501F atomic absorption spectrophotometer. The resdts are shown below.

Example 9

Acid enhanced gamma dvrmina oxide particles of samples Pbhk (AU), Pohk (AT), Pblk(CU), and Polk (CT) were made by procedures of Example 7. These materids were chahenged to determine the capacity of the dvimina to remove arsenic(As0₃ ^"2) given the variables in starting materids and treatment. A 200 ml portion of 1000 ppm of arsenic (arsenic trioxide in 10% nitric acid) standard (Fisher SA449-500) dhuted to 4 hters with deionized water was used. Ahquots (450 ml) of the resulting stock solution containing 50 ppm As, were tumbled for 24 h with duphcate approximately 2 ml (dry) volumes (both volume and mass measured) of each dumina sample, centrifuged, and stored prior to GFAA andysis. The instrument used was a Shimadzu AA-6501F atomic absorption spectrophotometer. The results are shown below.

Example 10

In a large scde test a 2,300 gallon tank was filled with approximately 2,000 gahons of tap water and 147.8 g of Pb(OAc)₂»3H₂O was added, the pH was adjusted to 6.7, and the tank was sampled and found to be 8,750 ppb in Pb⁺⁺. A canister was filled with 19.6 Kg of Polk (CT) as described in Example 7. The lead spiked water from the tank was pumped through the canister at a rate of 1.5 gahons per min. to remove the lead. Samples of the effluent were cohected after each 250 gallons and the lead concentration was determined and plotted as shown in Figure 1. The tank was refilled with another approximately 2,000 gahons of tap water and 147.8 g of Pb(OAc)₂»3H₂O was added to give a 9,160 ppb solution. The pH was adjusted to 7.00 and the spiked solution was pumped through the same canister at a flow rate at 1.5 gahons per min. Samples of the effluent were cohected after each 250 gahons and the lead concentration was determined and plotted as shown in Figure 1. Samples lead concentration for samples obtained at 2,000 - 3,500 were found to be below the detection limit of 0.2 ppb. The lead removd capacity of Polk (CT) was deteπ ined in this test to be 6 g/Kg.

Example 11

Various adsorbent and/or catdytic binder systems as set forth in Table 10 in Example 12 below were made in accordance with the generd procedures of this invention as fohows as weh as various systems not a part of the invention.

The binder and adsorbent and/or catdytic particles were combined into a mixing vessel, the amount of each varied according to the size batch desired. However, the component ratios remained constant as indicated in Table 10 below. This "dry" combination was pre-mixed to ensure a homogenous mixture of ah of the components. After this was accomphshed, a solution containing 5% acetic acid in disthled water was added to the mixture. The amount of the acid compared to the other components varied depending on extruding parameters and other processing variables, but for the procedures herein the range was typicahy between 35 and 45 wt. % of the totd mixture.

This solution was added to the dry materids and mixed unth the materid had a homogenous "modeling clay" like consistency. The mixing was performed utilizing a Hobart "A-300" mixer. The materid was then ready for extrusion. The mixed product containing the acetic acid solution was fed through an extruder, such as a DGL-1 dome granulator manufactured by LCI Corporation of Charlotte, N.C., U.S.A. The extrudates were fed through a QJ-230 marumarizer, dso manufactured by LCI Corporation, which turned the extrudates as "Rods" into smah spheres. The extruding and marumarizing steps provided a finished product suitable to use for a specific apphcation. However, the marumarizing is optiond and does not dter the performance of the product. After the spheres were made, the product was transferred to a drying oven where it was dried for one (1) hour at a temperature of 250° Celsius. The product was then ready for use in an apphcation. Example 12

The particles as formed of the constituents hsted below in Table 10 were tested for their ability to remove TCE. Adsorbent and/or catdyst and binder systems of Table 10 were chahenged with various concentrations of TCE as indicated in Table 10. Two custom made columns (40 cmX 20 mm) equipped with coarse glass frits were dried packed with 10 mL volumes (measured with a 10 mL graduated cylinder) of particles. The columns were chahenged with five 10 mL ahquots (5 bed volumes) of the trichloro ethylene (TCE) solution. The fifth bed volume from each column was cohected in a 50 mL Erlenmeyer flask, stoppered, and immediately andyzed by purge and trap-GC/MS technique using a Finnigan MAT Magnum ion trap GC MS equipped with a Tekmar hquid sample concentrator (LSC 2000).

The particles in Table 10 were prepared as described in Example 11. The percent composition of each component as weh as the nature of the binder are presented in Table 10. Prior to mixing with the other components, the duminum oxide particle was first cdcined at 500°C or 550°C as indicated in Table 10, then acid treated by substantially contacting with 0.5% acetic acid at room temperature for 15 minutes as generally set forth in applicants' copending apphcation filed on even date entitled "Acid Contacted Enhanced Adsorbent Particle and Method of making and Using Therefor" and as set forth in the parent apphcations to that apphcation as hsted above, and then dried at 121 °C for 90 minutes.

The removd of TCE from aqueous solution was investigated using a number of adsorbent and/or catdyst and binder systems of the present invention, and these results are summarized in Table 10. In Entry 8, 99% reduction of TCE was observed when the particle consisted of 40% CuO, 40% MnO₂, and 20% cohoidd dumina as the binder. When no binder was used, however, the CuO/MnO₂ particle removed only 0-1% of TCE (Entries 9A 9B). These results indicate the necessity of the binder materid to enhance or provide adsorbent and/or catdytic properties of or to the particle. Other particles demonstrated the ability to remove TCE. For example, entry 1 removed > 95% of TCE. Entry 7 removed 99% of TCE. The particle of entry 7 had two adsorbent and/or catdyst particles, one of which was carbon. Carbon was dso used in conjunction with multiple metd oxide components (Entry 24A and B) to remove TCE (>90%).

Although Entry 3 removed 96% of TCE, the PVP binder does not hold the particle together as long as the binders of the present invention. Particles with the PVP binder disintegrated over time, which reduced the usefulness of the particle. In the case of Entries 5A, 5B and 6, TCE removd was very high (98%); however, the activated peat dso breaks apart much faster than the particles of the present invention. The contaminents adsorbed by the peat may dso leach into the envhonment.

Not wishing to be bound by theory, two plausible mechanisms can account for the catdytic degradation of TCE using the particles of the present invention. The first mechanism involves redox chemistry between TCE and the metd oxide components of the particle. TCE is electrophilic, and can stabilize a negative charge if reduced. Electron transfer from a metd oxide component to TCE may be the first step toward the degradation of TCE. A second mechanism involves a Lewis acid-base interaction between TCE and the metd oxide component, which increases the rate of nucleophihc attack of TCE by water. Due to the lone pair electrons on the chlorine groups of TCE, a metd oxide component can initially coordinate to the chlorine group. This initid coordination may dso be the first step toward the catdytic degradation of TCE.

* sample did not allow water flow

** particle fell apart upon use PVP = GAFPVPK-60Polyvinylpyrrolidone V-900 = aRoche V-900 gd -Jumuia (colloidal alumina)

Sol P2 = Condea Disperal Sol P2 (colloidal alumina) Zeolite = Zeolyst international CBV 100 CuO = Fisher C472 Mn0₂= Kerr-McGee KM® Electrolytic Manganese Dioxide 92 % Mn02 X-ray powder diffradfi studies indicate this to be a mixture of manganese oxides.

Tin=FisherT128 Zinc = Fisher Zl 6

MelhylCellulose = Fisher M352 WHP Carbon = Calgon WPH powdered activate carbon # particle heated to 550° C in air to convert Mn0₂ to Mn₃0₄

NA = not applicable

Example 13

Various adsorbent and/or catdyst and binder systems of Table 11 were prepared according to the procedures of Examples 11 and Example 12 (duminum oxide preparation). Samples were tested to deteπnine if they reacted with hydrogen sulfide at room temperature. Hydrogen sulfide was generated by treating sodium sulfide with sulfuric acid and vacuum transferred into an TR ceh which had been loaded with 1.00 g of adsorbent and/or catdyst binder system to be tested. The IR ceh used was 9 cm long by 4 cm in diameter (-120 mL volume). The ceh was filled to approximately 170 toιτ H₂S and observed visually and IR spectra recorded.

The percent composition of each component as weh as the nature of the binder are presented in Table 11. The duminum oxide particle was first cdcined at 550° , then acid treated using 0.5% acetic acid and dried at 121 °C for 90 minutes using the same procedure described in Example 12. The cross-linking temperature for each particle was 250 °C for 1 hour.

The removd of hydrogen sulfide using the adsorbent and/or catdyst and binder systems of the present invention was investigated, and these results are summarized in Table 11. The removd of hydrogen sulfide by the adsorbent and/or catdyst binder systems was monitored by infrared spectroscopy. Based on these results, adsorbent and/or catdyst and binder systems of cohoidd duminum binder, acid treated duminum oxide, and copper oxide provided the best results with regards to the removd of hydrogen sulfide.

A1₂0₃= calcined at 550 °C and then acid treated

N-900 = LaRoadh N-900 gel alumina (colloidal alumina)

Example 14

TCE adsorption and TCLP extraction procedures were performed as fohows. A 20.0114-gram (about 24.50 mL bed volume) sample of the cohoidd dumina and Al₂O₃/CuO MnO₂ combination particle of Table 11, entry 1, dter treatment with TCE was wet packed into a 50-mL buret (with removable stopcock) plugged with glass wool. The sample was charged with five bed volumes of water. The sorbent materid was then quantitatively transferred into the Zero Headspace Extractor (ZHE) apparatus into which 200 mL of water was added, appropriately seded and agitated for 18 hours. The filtered solution was cohected in two 100 mL vids, stored in the refrigerator at

4°C unth andysis by GC/MS. The Finnigan MAT Magnum ion trap GC/MS equipped with a Tekmar hquid sample concentrator (LSC 2000) was used for andysis.

The calibration curve procedure was as fohows. A freshly prepared 50 ppm TCE stock solution was obtained by dissolving 34.2 μl spectrophotometric grade TCE

(Aldrich) in 20 ml HPLC grade methanol (Fisher) fohowed by dilution to a hter. Dhution of this solution (1000 μl : IL) resulted in a 50 ppb TCE stock solution. Ah dhutions were accomphshed using deionized water. A calibration curve was constructed by purging 1.0, 0.50, 0.20, 0.10, and 0.050 ppb TCE solutions.

The results are set forth below in Table 12.

Not detected. The fact that TCE in the sample is less that 500 ppb (EPA TCLP hmit) characterizes it as a nonhazardous waste with respect to TCE.

Example 15

Adsorbent and/or catdyst and catdyst supports were prepared as described in Example 11 utilizing Bayerite dumina (cdcined 550° C for 1 hr, then treated with 0.5% acetic acid for 15 min), 25% by weight cohoidd dumina, using 7 % HNO₃, 1 hour curing time, extruded and cured at temperatures of 300°, 350°, 400°, 450°, 500°, 550°, 600 °, and 650°. Table 13 gives the curing temperature and properties of these materids deteπnined by BET surface area measurements, mercury porosimetry and thermd gravometeric andysis.

Example 16

Various adsorbent and/or catdyst and catdyst supports were formed as described in Example 11 utilizing Bayerite dumina (cdcined 550° C for 1 hr, then treated with 0.5% Acetic Acid for 15 min.), 25% cohoidd dumina, using 7 % acetic acid, 1 hour curing time, extruded and cured at temperatures of 300°, 350°, 400°, 450°, 500°, and 600°. Table 14 give the curing temperature and properties of these materids deteπnined by BET surface area measurements, mercury porosimetry and thermd gravometeric andysis.

Figure 2 gives the surface area of Alumina- Alumina composites prepared as described in Experiment 15 and 16 as a function of curing temperature. Figure 2 dso gives the surface area the particle upon curing for 7 hours and 14 hours). In addition, Figure 2 gives the surface area of Alumina- Alumina composites prepared as described in Experiments 15 and 16, upon curing for 2 hours and 4 hours at 350° C.

The data in Tables 13 and 14 and Figure 2 indicate how the surface area, surface morphology and acid properties (Lewis vs Bronsted sites) can be controhed by this invention. The surface area, pore area, bulk density, skeletd density, porosity, and acid properties obtained are dependent upon curing time and curing temperature.

TABLE 13

Characterization of Alumina- Alumina Composite

Starting Material: Bayerite (cdcined 550° C for 1 hr, then treated with 0.5% acetic acid for 15 min.)

% Binder: 25 weight %

Curing Temperature: Variable

Curing Time: lHr

Acid Type (concentration): HNO₃ (7 %)

TABLE 14

Characterization of Alumma- Alumina Composite

Starting Material: Bayerite (cdcined 550° C for 1 hr, then treated with 0.5% acetic acid for 15 min. )

% Binder. 25 weight %

Curing Temperature: Variable

Curing Time: lHr

Acid Type (concentration): HOAc (7 %)

Example 17

A CuO/MnO₂/Al₂O₃-cohoidd ALO₃ binder 5/5/70/20 weight % catdyst was prepared as described in Example 11. The catdyst (0.933 g) was loaded into a "ϋ- tube" flow reactor, was attached to a gas cylinder with a synthetic mixture of 60 ppm of CO, and 0.6 % pentane in air. The CO/pentane/air mixture was passed over that catdyst with a flow rate of 80 mL/ in. Figure 3 gives a plot of CO concentration and temperature vs time. The data indicate that their is an induction period, after which the catdyst oxidizes CO at room temperature.

Experiment 18

A CuO/Ga₂O₃/Al₂O₃-cohoidd Al₂O₃ binder 5/5/70/20 weight % catdyst was prepared as described in Example 11. The catdyst (1.007 g) was loaded into a 'TJ-tube" flow reactor, was attached to a gas cylinder with a synthetic mixture of 81 ppm of NO,

910 ppm CO in nitrogen. The NO/CO/nitrogen mixture was passed over that catdyst at a flow rate of 80 mL/min. Figure 4 gives a light-off curve deteπnined under these conditions.

Experiment 19

Runoff water was pumped through a 5-gahon canister of duminum oxide that was cdcined at 550° C for 2.5 hours then acid washed with a 0.5% solution of acetic acid. The water flow rate was approximately 1 gpm The pH was 8.5. After 24 hours or the equivdent of approximately 1,440 gahons of contaminated water the effluent was tested for uranium, and the results are in Table 15.

Example 20

A particle with the fohowing composition was prepared in a manner simhar to Example 13 in order to test its efficiency in removing chlorinated hydrocarbons from a ground water source: 60% Al₂O₃ (Acid enhanced dumina), 5% CuO, 10% MOLECULITE^®, 20% dumina binder (cohoidd dumina) and 10% carbon. A partid groundwater profile contained the fohowing contaminants at pH 6.7:

1 , 1 -Dichloroethene 7,100ppb Acetone 40,000

Methylene Chloride 90,000 1 , 1 -Dichloroethane 1100 1,1,1 -Trichloroethane 27,000 Trichloroethene 830 Toluene 1100 Tetrachloroethene 1400 Thirty three gahons of the binder and catdyst system was placed into a 55gahon drum. The groundwater was pumped through the media at a rate of 4 gp The effluent was andyzed for volathe organics after pumping 40,320 and 70,000 gahons of the groundwater. The results are shown in Table 16.

These results demonstrate that the level of chlorinated hydrocarbons in the groundwater were reduced significantly when the groundwater was contacted with the binder and catdyst system.

Example 21

Using the identicd binder catdyst system in Example 20, the removd of tetrachloroethene from ground water was investigated. A 55-gdlon drum was filled with 36 gdlons of the binder catdyst system. The contaminated water was pumped from three wells through the media at a combined flow rate of approximately 4gpm. The pH of the ground water was 6.5. Approximately 90,000 gdlons of contaminated water had been pumped through the binder catdyst system. The results of the experiment are shown In Table 17.

The increase in concentration of cis-1, 2-dichloroethene is a result of and an indication of the degradation of tetrachloroethene. Cis- 1 ,2-dichloroethene is an intermediate product of the degradation of tetrachloroethene, which is a non-hazardous waste materid.

Throughout this apphcation, various pubhcations are referenced. The disclosures of these pubhcations in their entireties are hereby incorporated by reference into this apphcation in order to more fully describe the state of the art to which this invention pertains.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or sphit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the fohowing claims.

Claims

What is claimed is:

1. A process for producing an acid enhanced adsorbent particle comprising contacting a particle comprising a non-amorphous, non-ceramic, crystalline, porous, cdcined, duminum oxide particle that was produced by cdcining at a particle temperature of from 300° C to 700 °C, with a dhute acid for a sufficient time to increase the adsorbent properties of the particle, wherein the acid contacting is more than a surface wash but less than an etcMng of the particle, wherein the resultant acid treated duminum oxide is not subsequently cdcined.

2. The method of Claim 1, wherein the particle temperature is from 400°C to 700 °C.

3. The method of Claim 1, wherein the acid comprises an aliphatic or aryl carboxylic acid.

4. The process of Claim 1, wherein the acid comprises acetic, nitric, suhuric, hydrochloric, boric, formic, or phosphoric acid, or mixtures thereof.

5. The process of Claim 1, wherein the acid comprises acetic acid.

6. The process of Claim 1, wherein the contacting is by dipping or submerging the particle in acid.

7. The process of Claim 1, further comprising the step of rinsing the particle to remove excess acid.

8. The process of Claim 1, further comprising the step of drying the particle.

9. The process of Claim 7, wherein the contacting is for at least 15 minutes.

10. The process of Claim 1, wherein the dhute acid strength is equivdent to an aqueous acetic acid solution at less than or equd to 0.09 N.

11. The process of Claim 1, wherein the dhute acid strength is equivdent to an aqueous acetic acid solution at less than or equd to 0.02 N.

12. The process of Claim 1, wherein the dhute acid strength is equivdent to an aqueous acetic acid solution at less than or equd to 0.01 N.

13. The process of Claim 1, wherein the dhute acid strength is equivdent to an aqueous acetic acid solution at less than or equd to 0.005 N.

14. The process of Claim 1, wherein the dhute acid strength is equivdent to an aqueous acetic acid solution at less than or equd to 0.001 N.

15. The process of Claim 1, wherein the cdcined duminum oxide is in the gamma, chi-rho, or eta form

16. The process of Claim 1 , wherein the duminum oxide prior to or after acid treatment is not sintered.

17. The process of Claim 1, wherein the particle consists essentially of duminum oxide.

18. The process of Claim 1 , wherein the particle consists of duminum oxide.

19. The process of Claim 1, wherein the resultant acid treated duminum oxide is substantially microporous.

20. The process of Claim 1, wherein the duminum oxide is not an adsorbent or catdyst support.

21. A process for producing an acid enhanced adsorbent particle consisting essentially of contacting a particle comprising a non-amorphous, non-ceramic, crystalline, porous, cdcined, duminum oxide particle that was produced by calcining at a particle temperature of from 300° C to 700° C, with a dhute acid for a sufficient time to increase the adsorbent properties of the particle, wherein the acid contacting is more than a surface wash but less than an etching of the particle.

22. The particle made by the process of Claim 1.

23. The particle made by the process of Claim 5.

24. The particle of Claim 22, wherein sdd particle passes the EPA TCLP test for a particular cont-iminant.

25. The particle of Claim 24, wherein sdd cont-tminant is lead.

26. A process for reducing or eliminating the amount of contaminants in a hquid or gas stream comprising contacting the particle of Claim 22 with the hquid or gas stream for a sufficient time to reduce the amount of or eliminate the contamination from the hquid or gas strea

27. The process of Claim 26, wherein the stream is hquid.

28. The process of Claim 26, wherein the stream is gas.

29. The process of Claim 26, wherein the contaminant is lead, phosphate, selenium, or zinc.

30. The process of claim 26, wherein the contaminant comprises an anion, an oxoanion, a cation, or a poly-oxoanion.

31. A method of encapsulating a contaminant within an adsorbent particle comprising heating the particle of Claim 22 that has adsorbed a cont-iminant to a temperature sufficient to close the pores of the particle to thereby encapsulate the contaminant within the particle.

32. A method of encapsulating a contaminant within an adsorbent particle comprising heating the particle that has adsorbed a contaminant to a temperature sufficient to close the pores of the particle to thereby encapsulate the cont-αriinant within the particle, wherein the particle is produced by the process comprising contacting a particle comprising a non-ceramic, porous, oxide adsorbent particle with a dhute acid for a sufficient time to increase the adsorbent properties of the particle, wherein the acid contacting is more than a surface wash but less than an etching of the particle, wherein the oxide adsorbent particle is not duminum oxide and wherein the resdtant acid treated oxide adsorbent particle is not subsequently cdcined.

33. The method of Claim 22, wherein the temperature is from 450 ° C to 2000 ° C.

34. A method for regenerating the system of Claim 22 that has adsorbed a contaminant, comprising thermahy oxidizing sdd system or contacting sdd system with (1) a reagent wash comprising aqueous -immonia, a phosphine, a detergent or a mixture thereof; (2) an acid or base to cause a pH swing; (3) or a Lewis acid or base.

35. A method for regenerating the system that has adsorbed a contaminant, comprising therma y oxidizing sdd system or contacting sdd system with (1) a reagent wash comprising aqueous ammonia, a phosphine, a detergent or a mixture thereof; (2) an acid or base to cause a pH swing; (3) or a Lewis acid or base, wherein the system is produced by the process comprising contacting a particle comprising a non-ceramic, porous, oxide adsorbent particle with a dhute acid for a sufficient time to increase the adsorbent properties of the particle, wherein the acid contacting is more than a surface wash but less than an etching of the particle, wherein the oxide adsorbent particle is not dirminum oxide and wherein the resultant acid treated oxide adsorbent particle is not subsequently cdcined.

36. A composition comprising the duminum oxide particle made by the process of Claim 1.

37. The composition of Claim 36, further comprising a second oxide adsorbent particle.

38. The composition of Claim 37, further comprising a cross-linked cohoidd duminuin oxide binder.

39. The composition of Claim 36, further comprising silicon dioxide, manganese oxide, copper oxide, vanadium pentoxide, zirconium oxide, iron oxide or titanium dioxide.

40. The composition of Claim 36, further comprising a zeohte.

41. The composition of Claim 36, further comprising copper oxide and manganese oxide, wherein sdd copper oxide and sdd manganese oxide have not been acid enhanced.

42. The composition of Claim 41, wherein the composition comprises 50-98 parts by weight of sdd acid enhanced duminum oxide, 1-49 parts by weight of sdd copper oxide, and 1-49 parts by weight of sdd manganese oxide.

43. The composition of Claim 42, wherein sdd copper oxide is CuO and sdd manganese oxide is Mh0₂.

44. The composition of Claim 41, wherein sdd composition passes the EPA TCLP test for trichloro ethylene.

45. The composition of Claim 36, further comprising a noble metd.

46. The composition of Claim 36, further comprising a catdyst particle.

47. The composition of Claim 36, further comprising an adsorbent particle.

48. A process for reducing or eliminating the amount of an organic contaminant in a hquid or gas stream comprising contacting the composition of Claim 41 with the hquid or gas stream for a sufficient time to reduce the amount of or eliminate the organic contaminant from the hquid or gas stream.

49. The process of Claim 48, wherein the organic contaminant is a chlorinated organic.

50. The process of Claim 48, wherein the organic contaminant is trichloroethylene.

51. The process of Claim 48 , wherein sdd reduction or ehmination is by a catdytic degradation process.

52. A composition comprising (1) a particle made by the process comprising contacting a particle comprising a non-amorphous, non-ceramic, crystalline, porous, cdcined, duminum oxide particle that was produced by cdcining at a particle temperature of from 300° C to 700° C, with a dhute acid for a sufficient time to increase the adsorbent properties of the duminum oxide particle and (2)

• copper oxide and (3) manganese oxide, wherein sdd copper oxide and sdd manganese oxide have not been acid enhanced.

53. The composition of Claim 52, wherein the particle temperature is from 400° to 700 °C.

54. The method of Claim 1 , wherein the particle, prior to contacting with the acid, further comprises a second type of adsorbent and/or catdytic particle and further comprises a binder comprising a cohoidd metd oxide or cohoidd metahoid oxide.

55. The method of Claim 54, wherein the binder is cross-linked to at least one of the particle types or to itself.

56. The method of Claim 1, further comprising,

(1) mixing the resultant particle of Claim 1 with at least one other type of adsorbent and/or catdyst particle, a binder comprising cohoidd metd oxide or cohoidd metahoid oxide, and an acid; and

(2) heating the mixture to a sufficient temperature for a sufficient time to cross-link the binder to at least one type of particle or to itself.

57. The method of Claim 56, wherein the heating step is from 25 °C to 400°C.

58. The method of Claim 56, wherein the heating step is from 70°C to 150°C.

59. An adsorbent and/or catdyst and binder composition comprising the particle made by the process of Claim 1 and further comprising a second type of adsorbent and/or catalyst particle and a binder comprising cohoidd metd oxide or cohoidd metahoid oxide.

60. The composition of Claim 59, wherein the binder is cross-linked to at least one of the particle types or to itself.

61. A process for producing an adsorbent and/or catdyst compound, comprising,

(1) iriixing an acid enhanced particle prepared by contacting a particle comprising a non-ceramic, porous, oxide adsorbent particle with a dhute acid for a sufficient time to increase the adsorbent properties of the particle, wherein the acid contacting is more than a surface wash but less than an etching of the particle, wherein the oxide adsorbent particle is not duminum oxide and wherein the resultant acid treated oxide adsorbent particle is not subsequently cdcined, with at least one other type of adsorbent and/or catdyst particle, a binder comprising cohoidd metd oxide or cohoidd metahoid oxide, and an acid; and

62. A method for producing an adsorbent and/or catdyst and binder system comprising (i) mixing components comprising

(a) a binder comprising a cohoidd metd oxide or cohoidd metahoid oxide,

(b) an oxide adsorbent and/or catdyst particle, and

(c) an acid,

(ii) removing a sufficient amount of water from the mixture to cross-link components a and b to form an adsorbent and/or catdyst and binder system,

wherein component b comprises a particle of an oxide of cdcium, strontium, barium, boron, gaffium, indium, thalhum,

tin, bismuth, or a non-amorphous, non-ceramic, crystalline, porous, cdcined duminum. oxide particle that was produced by cdcining the precursor to the cdcined duminum oxide at a particle temperature of from 300 °C to 700 °C. or a mixture thereof.

63. The method of Claim 62, wherein when component b is cdcined dirminum oxide, the cdcined duminum oxide particle is in the gamma, chi-rho, or eta form.

64. The method of Claim 63, wherein the cdcined duminum oxide particle was pretreated with an acid activation treatment.

65. A method for producing an adsorbent and/or catdyst and binder system comprising

(i) mixing components comprising

(a) a binder comprising a cohoidd metd oxide or cohoidd metahoid oxide,

(b) an oxide adsorbent and/or catdyst particle, and

(c) an acid, (ii) removing a sufficient amount of water from the mixture to cross-link components a and b to form an adsorbent and/or catdyst and binder system, wherein the acid comprises an aliphatic or aryl carboxyhc acid.

66. The method of Claim 65, wherein the acid comprises acetic acid, benzoic acid, butyric acid, citric acid, fatty acids, lactic acid, mdeic acid, mdonic acid, oxahc acid, salicylic acid, stearic acid, succinic acid, tartaric acid, propionic acid, vderic acid, hexanoic acid, heptanoic acid, capryhc acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, trideconoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, triosanoic acid, hgnoceric acid, pentacosanoic acid, cerotic acid, heptasauoic acid, montanic acid, nonacosanoic acid, mehssic acid , phthalic acid, glutaric acid, adipic acid, azeldc acid, sebacic acid, cinnamic acid, acryhc acid, crotonic acid, linoleic acid or a mixture thereof.

67. A method for producing an adsorbent and/or catdyst and binder system comprising

(i) mixing components comprising

(a) a binder comprising a cohoidd metd oxide or cohoidd metahoid oxide,

(b) an oxide adsorbent and/or catdyst particle, and

(c) an acid,

(ii) removing a sufficient amount of water from the mixture to cross-link components a and b to form an adsorbent and/or catdyst and binder system, wherein the removing step comprises heating the system from 70°C to 150°C.

68. The method of Claim 67, wherein the binder is cohoidd dumina.

69. An adsorbent and/or catdyst and binder system comprising a binder that has been cross-linked with at least one type of oxide adsorbent and/or catdyst particle, wherein the binder comprises a cohoidd metd oxide or cohoidd metahoid oxide, wherein the oxide adsorbent and/or catdyst particle comprises particles of an oxide of cdcium, strontium, barium, boron, gdhum, indium, thalhum, geπriamum, bismuth, a non-amorphous, non-ceramic, c stalhne, porous, cdcined duminum oxide particle that was produced by cdcining the precursor to the cdcined duminum oxide at a particle temperature of from 300 °C to 700 °C, or a mixture thereof.

70. The system of Claim 69 , wherein the particle temperature is from 400 ° C to 700°C.

71. The system of Claim 69 , wherein the cdcined duminum. oxide particle is in the gamma, chi-rho, or eta for

72. The system of Claim 71 , wherein the cdcined duminum oxide particle was pretreated with an acid activation treatment.

73. An adsorbent and/or catdyst and binder system comprising a binder that has been cross-linked with at least one type of oxide adsorbent and/or catdyst particle, wherein

(a) the binder is cohoidd dumina and the particle comprises duminum oxide, gallium oxide and copper oxide;

(b) the binder is cohoidd dumina and the particle comprises duminum oxide, and a mixed oxide comprising manganese dioxide, duminum oxide and copper oxide;

(c) the binder is cohoidd dumina and the particle comprises duminum oxide, copper oxide and zirconium oxide;

(d) the binder is cohoidd dumina and the particle comprises duminum oxide and silver nitrate;

(e) the binder is cohoidd dumina and the particle comprises duminum oxide, magnesium, oxide, manganese dioxide and copper oxide;

(f) the binder is cohoidd dumina and the particle comprises duminum oxide, copper oxide, and a mixed oxide comprising copper oxide, manganese dioxide, and hthium hydroxide;

(g) the binder is cohoidd dumina and the particle comprises duminum oxide, zinc oxide and copper oxide;

(h) the binder is cohoidd dumina and the particle comprises duminum oxide and copper oxide; or

(i) the binder is cohoidd dumina, and the particle comprises duminum oxide, mixed oxides of manganese, copper oxide, and carbon.

74. The system of claim 73, wherein when the binder is cohoidd dumina, and the particle comprises duminum oxide, mixed oxides of manganese, copper oxide, and carbon, the system further comprises hthium hydroxide.

75. The system of Claim 73, wherein when the binder is cohoidd dumina and the particle comprises duminum oxide, gallium oxide and copper oxide, the cohoidd dumina is from 1 to 97% by weight, the duminum oxide is from is from 1 to 97% by weight, the gallium oxide is from 1 to 97% by weight, and the copper oxide is from 1 to 97% by weight.

76. The system of Claim 73, wherein when the binder is cohoidd dumina and the particle comprises durriinum oxide, ga ium oxide and copper oxide, the cohoidd diimina is from 5 to 40% by weight, the duminum oxide is from is from 40 to 97% by weight, the galhtrm oxide is from 1 to 10% by weight, and the copper oxide is from 1 to 10% by weight.

77. The system of Claim 73, wherein when the binder is cohoidd dumina and the particle comprises duminum oxide, and a mixed oxide comprising manganese dioxide, duminum oxide and copper oxide, the cohoidd dumina is from 1 to 98% by weight, the duminum oxide is from is from 1 to 98% by weight, and the mixed oxide is from 1 to 98% by weight.

78. The system of Claim 73, wherein when the binder is cohoidd diimina and the particle comprises duminum oxide, and a mixed oxide comprising manganese dioxide, duminum oxide and copper oxide, the cohoidd dumina is from 10 to 40% by weight, the duminum oxide is from is from 10 to 40% by weight, and the mixed oxide is from 20 to 70% by weight.

79. The system of Claim 73, wherein when the binder is cohoidd dumina and the particle comprises durriinum oxide and copper oxide, the cohoidd dumina is from 1 to 98% by weight, the duminum oxide is from is from 1 to 98% by weight, and the copper oxide is from 1 to 98% by weight.

80. The system of Claim 73, wherein when the binder is cohoidd dumina and the particle comprises duminum oxide and copper oxide, the cohoidd dumina is from 10 to 40% by weight, the durώium oxide is from is from 30 to 70% by weight, and the copper oxide is from 1 to 20% by weight.

81. The system of Claim 73 , wherein when the binder is cohoidd dumina and the particle comprises duminum oxide, copper oxide and zhconium oxide, the ill

cohoidd dumina is from 1 to 97% by weight, the duminum oxide is from is from 1 to 97% by weight, and the copper oxide is from 1 to 97% by weight, and the zhconium oxide is from 1 to 97% by weight.

82. The system of Claim 73, wherein when the binder is cohoidd dumina and the particle comprises duminum oxide, copper oxide and zhconium oxide, the cohoidd dumina is from 10 to 40% by weight, the duminum oxide is from is from 30 to 70% by weight, and the copper oxide is from 10 to 20% by weight, and the zirconium oxide is from 1 to 20% by weight.

83. The system of Claim 73, wherein when the binder is cohoidd dumina and the particle comprises duminum oxide and silver nitrate, the cohoidd dumina is from 1 to 98% by weight, the duminum oxide is from is from 1 to 98% by weight, and the silver nitrate is from 1 to 98% by weight.

84. The system of Claim 73, wherein when the binder is cohoidd dumina and the particle comprises duminum oxide and silver nitrate, the cohoidd dumina is from 10 to 40% by weight, the duminum oxide is from is from 30 to 70% by weight, and the shver.nitrate is from 1 to 20% by weight.

85. The system of Claim 73, wherein when the binder is cohoidd dumina and the particle comprises duminum oxide, magnesium oxide, manganese dioxide and copper oxide, the cohoidd dumina is from 1 to 96% by weight, the duminum oxide is from is from 1 to 96% by weight, the magnesium oxide is from 1 to 96% by weight, the manganese dioxide is from 1 to 96% by weight, and the copper oxide is from 1 to 96% by weight.

86. The system of Claim 73, wherein when the binder is cohoidd dumina and the particle comprises duminum oxide, magnesium oxide, manganese dioxide and copper oxide, the cohoidd du ina is from 10 to 40% by weight, the duminum oxide is from is from 30 to 70% by weight, the magnesium oxide is from 1 to 30% by weight, the manganese dioxide is from 1 to 20% by weight, and the copper oxide is from 1 to 20% by weight.

87. The system of Claim 73, wherein when the binder is cohoidd dumina and the particle comprises duminum oxide, copper oxide, and a mixed oxide comprising copper oxide, manganese dioxide, and hthium hydroxide, the cohoidd dumina is from 1 to 97% by weight, the duminum oxide is from is from 1 to 97% by weight, the copper oxide is from 1 to 97% by weight, and the mixed oxide is from 1 to 97% by weight.

88. The system of Claim 73, wherein when the binder is cohoidd dumina and the particle comprises duminum oxide, copper oxide, and a mixed oxide comprising copper oxide, manganese dioxide, and hthium hydroxide, the cohoidd dumina is from 10 to 40% by weight, the duminum oxide is from is from 30 to 70% by weight, the copper oxide is from 1 to 20% by weight, and the mixed oxide is from 1 to 20% by weight.

89. An adsorbent and/or catdyst and binder system comprising a binder that has been cross-linked with at least one type of oxide adsorbent and/or catdyst particle, wherein the binder comprises a cohoidd metd oxide or cohoidd metahoid oxide, wherein the particle comprises Al₂O₃, Ti0₂, CuO, Cu^O, N₂O₅, Si0₂, MnO₂, Mn₂O₃, Mn₃O₄, ZnO, WO₂, WO₃, Re₂0₇, As₂0₃, As₂O₅, MgO, Th0₂, Ag₂O, AgO, CdO, SnO₂, PbO, FeO, Fe₂O₃, Fe₃0₄, Ru~O₃, RuO, OsO₄, Sb₂O₃, CoO, Co₂O₃, ΝiO, zeohte, or activated carbon.

90. The system of claim 89, wherein the particle further comprises a second type of adsorbent and/or catdyst particles of an oxide of duminum, titanium, copper, vanadium, silicon, manganese, hon, zinc, zirconium, tungsten, rhenium, arsenic, magnesium, morium, silver, cadmium, tin, lead, antimony, m erhum, osmium, cobdt or nickel or zeohte, activated carbon, including cod and coconut carbon, peat, zinc or tin.

91. The system of claim 89, wherein particle comprises duminum oxide, silicon dioxide and activated carbon.

92. An adsorbent and/or catdyst and binder system comprising a binder that has been cross-linked with at least one type of oxide adsorbent and/or catdyst particle, wherein (1) the binder comprises cohoidd silicon dioxide, cohoidd duminum oxide, or a combination thereof, and (2) the particle comprises duminum oxide, shicate, diatomaceous earth, or a combination thereof.

93. The system of claim 92, wherein the binder is cohoidd duminum oxide and the particle comprises d riinum oxide, shicate, and diatomaceous earth.

94. The system of claim 92, wherein the binder is cohoidd duminum oxide and the particle comprises duminum oxide and diatomaceous earth.

95. The system of claim 92, wherein the binder is cohoidd silicon dioxide and the particle comprises duminum oxide, shicate, and diatomaceous earth.

96. The system of claim 92, wherein the binder is cohoidd duminum oxide and cohoidd silicon dioxide and the particle comprises silicate and diatomaceous earth.

97. A method for reducing or eliminating the amount of a contaminant from a hquid or gas stream comprising contacting an adsorbent and/or catdyst and binder system comprising a binder that has been cross-hnked with at least one type of oxide adsorbent and/or catdyst particle, wherein the binder comprises a cohoidd metd oxide or cohoidd metahoid oxide, with the contaminant in the stream for a sufficient time to reduce or eliminate the amount of contaminant from the stream, wherein the contaminant comprises an anion, an oxo anion, a cation, or a poly-oxo anion.

98. A method of encapsulating a contaminant within an adsorbent particle comprising heating a system that has adsorbed a cont-iminant to a temperature sufficient to close the pores of the system to thereby encapsulate the cont-iminant within the system, wherein the system comprises an adsorbent and/or catdyst and binder system comprising a binder that has been cross-linked with at least one type of oxide adsorbent and/or catdyst particle, wherein the binder comprises a cohoidd metd oxide or cohoidd metahoid oxide.

99. The method of Claim 98, wherein the temperature is from 450°C to 2000°C.

100. A method for modifying the physicd property of a system comprising heating the system for a sufficient time to thereby modify the physicd property, wherein the system comprises an adsorbent and/or catdyst and binder system comprising a binder that has been cross-hnked with at least one type of oxide adsorbent and/or catdyst particle, wherein the binder comprises a cohoidd metd oxide or cohoidd metalloid oxide

101. The method of Claim 100, wherein the heating is performed to increase the surface area of the system.

102. The method of Claim 101 , wherein the physical property comprises surface area, pore area, bulk density, skeletd density or porosity.

103. A method for adsorbing an ion from a hquid or gas stream comprising contacting an adsorbent and/or catdyst and binder system comprising a binder that has been cross-linked with at least one type of oxide adsorbent and/or catdyst particle, wherein the binder comprises a cohoidd metd oxide or cohoidd metahoid oxide with a hquid or gas stream containing the ion.

104. The method of Claim 103, wherein the ion comprises an anion, a cation, an oxo- anion, a poly-oxoanion or a mixture thereof.

105. A method for regenerating an adsorbent and/or catdyst and binder system comprising a binder that has been cross-linked with at least one type of oxide adsorbent and/or catdyst particle, wherein the binder comprises a cohoidd metd oxide or cohoidd metahoid oxide that has adsorbed a contaminant, comprising thermahy oxidizing sdd system or contacting sdd system with (1) a reagent wash comprising aqueous ammonia, a phosphine, a detergent or a mixture thereof; (2) an acid or base to cause a pH swing; (3) or a Lewis acid or base.

106. An anchored adsorbent and/or catdyst and binder system, comprising:

(a) a binder, and

(b) an oxide adsorbent and/or oxide catdyst particle, and

(c) a metd complex, wherein component (a) is cross-linked with component (b), and wherein the metd complex (c) is bound directly to component (a) and/or (b).

107. A method for producing an adsorbent and/or catdyst and binder system comprising

(i) mixing components comprising

(a) a binder comprising a cohoidd metd oxide or cohoidd metahoid oxide,

(b) an oxide adsorbent and/or catdyst particle, and

(c) an acid,

(ii) removing a sufficient amount of water from the mixture to cross-link components a and b to form an adsorbent and/or catdyst and binder system, further comprising binding a metd complex directly onto the resulting system of step (h) to form an anchored catdyst system.

108. The particle made by the process of Claim 107.

109. An adsorbent and/or catdyst and binder system, comprising:

(a) a pendant hgand substituted or unsubstituted binder, and

110. The system of claim 109, wherein the pendant hgand comprises one or more chird carbon, sulfur, nitrogen, phosphorous, or silicon centers, or a combination thereof.

111. The system of claim 109, wherein the chird hgand is an amino acid.

112. An anchored adsorbent and/or catdyst and binder system, comprising:

(a) a pendant hgand substituted or unsubstituted binder;

(b) a pendant hgand substituted or unsusbtituted oxide adsorbent and/or oxide catdyst particle; and

(c) a metd complex, wherein at least one of components (a)-(c) is a chird pendant hgand substituted, wherein component (a) is cross-linked with component (b), and wherein the metd complex (c) is bound to component (a) and/or (b).

113. A chromatograpy column comprising the adsorbent and/or catdyst and binder system of claim 109.

114. A chromatograpy column comprising the adsorbent and/or catdyst and binder system of claim 112.

115. A method for separating at least one compound from a mixture comprising two or more compounds, comprising contacting the mixture with the adsorbent and/or catdyst and binder system of claim 109.

116. The method of claim 115, wherein when the mixture is a racemic mixture, the system can separate one enantiomer from the other enantiomer.

117. A method for separating at least one compound from a mixture comprising two or more compounds, comprising contacting the mixture with the adsorbent and/or catdyst and binder system of claim 112.

118. The method of claim 117, wherein when the mixture is a racemic mixture, the system can separate one enantiomer from the other enantiomer.

119. A method for producing a pendant hgand substituted adsorbent and/or catdyst system, comprising:

(i) mixing components, comprising:

(a) a pendant hgand substituted or unsubstituted binder comprising a cohoidd metd oxide or a cohoidd metalloid oxide, (b) a pendant hgand substituted or unsubstituted oxide adsorbent and/or oxide catdyst particle, and

(c) a base,

wherein at least one of components (a) and (b) is pendant hgand substituted, and

(h) removing a sufficient amount of water from the mixture to cross-hhk components (a) and (b) to form a pendant hgand substituted adsorbent and/or catdyst and binder system.

120. The method of claim 119, wherein the component (a) and/or (b) has at least one chird center.

121. A method for producing a pendant hgand substituted adsorbent and/or catdyst system, comprising:

(i) ^• lTiixing components, comprising:

(a) a pendant hgand substituted or unsubstituted binder comprising a cohoidd metd oxide or a cohoidd metahoid oxide,

(b) a pendant hgand substituted or unsubstituted oxide adsorbent and/or oxide catdyst particle, and

(c) a metd complex, and

(d) a base, wherein at least one of components (a) and (b) is pendant hgand substituted, and

(ii) removing a sufficient amount of water from the mixture to cross-hhk components (a) and (b), wherein component (c) is bound to component (a) and/or (b) to form a pendant hgand substituted adsorbent and/or catdyst and binder system.

122. The method of claim 121, wherein the component (a), (b), and/or (c) has at least one cliird center.

123. A method for producing a composition containing an adsorbent and/or catdyst compound comprising:

(a) mixing components comprising

(i) a pendant hgand substituted binder comprising a cohoidd metd oxide or a cohoidd metahoid oxide,

(ii) an oxide adsorbent and/or catdyst particle comprising a cdcined, metd oxide particle that was produced by cdcining the particle temperature of from 300 °C to 700° C, then treating the cdcined particle with an acid for a sufficient time to increase the adsorbent properties of the particle, and

( i) water,

(b) removing a sufficient amount of water from the mixture to cross-link component i to itself, thereby entrapping and holding component ii within the cross-linked binder, to form an adsorbent and/or catdyst and binder system.

The method of claim 123, wherein the component i has at least one chhd center.