CA2227428A1

CA2227428A1 - Enhanced adsorbent and room temperature catalyst particle and method of making and using therefor

Info

Publication number: CA2227428A1
Application number: CA002227428A
Authority: CA
Inventors: Mark L. Moskovitz; Bryan E. Kepner
Original assignee: Mark L. Moskovitz; Bryan E. Kepner; Project Earth Industries, Inc.; M And K Patent Company, Inc.
Current assignee: Project Earth Industries Inc
Priority date: 1995-04-21
Filing date: 1996-04-17
Publication date: 1996-10-24
Also published as: MX9708060A; ZA963056B; WO1996033013A3; EP0865315A2; AU710253B2; IL117963A0; AU5551696A; NZ306840A; IL117963A; KR19990007944A; JPH11503964A; BR9608145A; WO1996033013A2; PL322886A1

Abstract

A method for producing an enhanced adsorbent and/or enhanced catalytic particle and/or for producing a catalytic particle, comprising the steps of:
(a) removing an effective amount of air from a closed chamber containing an adsorbent and/or catalytic particle, wherein the resultant chamber pressure is less than one atmosphere; (b) raising the chamber pressure with an inert gas to at least one atmosphere; (c) contacting the particle with an energy beam of sufficient energy for a sufficient time to thereby enhance the adsorbent and/or catalytic properties of the particle and/or produce catalytic properties in the particle. A continuous process directed to step (c) alone is also provided. Also disclosed are adsorbent and/or catalytic particles, methods of contaminant reduction or elimination, including room temperature catalysis, particle binders, apparatuses of the present invention, and methods of increasing the surface area of adsorbent and/or catalytic particles.

Description

EN~lANCED ADSORBENT AND ROOM TEMPERATURE
CATALYST PARTICLE AND
METHOD OF MAKING AND USING l~Rli ~OR

S BACKGROUND OF TElE INVENTION

I~IELD OF T~E INVENTION

This invention relates generally to adsorbent particles that have i~--p~ved 10 adsorbent pl ope- ~ies and/or i,..~. o~ed or newly existing catalytic p. upt;- ~ies, incl.lflinp room temperature catalyltic capability.

BACKGROUND ART

Oxides of metals and certain non-metals are known to be useful for removing conctitu~ntc from a gas or liquid stream by adsorbent . .~ c "c For PY~mple~ the use of activated ~ min~ is con~id~red to be an econo. :c~l method ~or treating water for the removal of a variety of polll~t~nt~, gasses, and some liquids. Its highly porous structure allows for p,~re,e"lial adso,~Li~e capacity for moisture and 20 co..ln ;~ cont~ined in gasses and some liquids. It is useful as a de~ cc~l for gasses and vapors in the petroleum industry, and has also been used as a catalyst or catalyst-carrier in air and in water purific~tiQn Removal of co ~ such as phosphates by activated ~ min~ are known in the art See, for ~y~mple~ Yee, W, "Selective Removal of Mixed Phosphates by Activated ~ min~," J.Amer. Waterworks Assoc., Vol 58, pp 25 239-247 (19~6).

U S Patent No 5,242,879 to Abe et aL discloses that activated carbon materials, which have been subjecl:ed to carbonization and activation tre~tm~nte~ and 30 then further subjected to an acid Lle~ -l and a heat l,e~ in an atmosphere comprising an inert gas or a reducing gas, have a high catalytic activity and are suitable as catalysts for the decomposition of hydrogen peroxide, hyd~ es or other water pollutants such as organic acids, quaternary ~mmonium-salts, and sulfur-co.~l~il i g SU~llll~lk ~H~tl (R~JLE2G~

W O96/33013 PCTrUS96/05303 compounds. Acid is used to remove impurities and not to ~nh~nce the adso r~LUI~s.

Ion illlplallLalion has been used in integrated circuit fabrication. U.S.
5 Patent No. 4,843,034 to Herndon et al. tliecloses methods and systems for fabricating interlayer conductive paths in integrated circuits by implanting ions into selected regions of normally insulative layers to change the composition and/or structure of the ine~ tit~n in the selected regions. It is stated that a wide range of insulative materials can be rendered selectively conductive, inclllding polymeric inelll~tors and inorganic inclll~tors, 10 such as metal or semi-con~1~lctQr oxides, nitrides or carbides. Tne~ tors which can be processed according to this patent include silicone dioxide, silicon nitride, silicon carbide, ~Illmimlm oxides, and others. It is ~lieclosed that ;",plA..~ed ions can include ions of silicon, gel",~"i~lm~ carbon, boron, arsenic, phosphorous, tit~nillm, molybdenum, ~Illmimlm, and gold. Typically, the imrl~nt~tion energy varies from about 10 to about 15 500 KeV. It is disclosed that the ion impl~nt~tion step changes the composition and structure of the insulative layer and is believed also to have the effect of diepl~ing oxygen, nitrogen, or carbon so as to promote the migration and alloying of metal from the conductive layer(s) into the imrl~nted region during the ~illL~ g step. The i llpl~ll~Lion also is believed to have the physical effect of di~lupL;Ilg the crystal lattice, 20 which may also f~rilit~te the fusion of the metal. This results in a composite material in the impl~nt~tion region çeeenti~lly col1~;e~ g ofthe disruptive inelll~tor and ;",p~ ed ions. In the working examples, ions of silicon were imrl~nted into the particular region of the silicon dioxide layer using a direct ;" ,pl~ ;on m~chine U.S. Patent No. 5,218,179 to Matossian et aL diecloses a plasma source arrangement for providing ions for ;..,?l~"l~;on into an object. A large scale object which is to be imrl~nted with ions is enclosed in a conla;ller. The plasma is genel~d in a chamber which is se~ le from, and opens into the co"~ r for a plasma source ion imrl~nt~tion working volume. The plasma defuses from the ch~lll)el into the container 30 to surround the object with substantially improved density colllp~ued to conventional tSb~tl (RULE26) W O96/33013 PCTrUS96/05303 practice. High voltage negative pulses are applied to the object, causing the ions ~o be accelerated from the plasma toward and be ;,.,p~ ed into the object.

Thus, there has been a need in the art for adsorbents that have improved S ability to adsorb particular m~teri~l~ especially co~ "l~; from a gas or liquid stream, to thereby purify the stream. 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 Co.~ s into non-co~ .l by-products.

Additionally, there has been a need in the art for adequately ~gglolll~ ing adsorbent particles together to form a composite particle for pe,ro".~i"g eiml~lt~n~o~l~ multiple applicati.ons and purifications. In the prior art, particles have been ground up and extruded together to hold them in an agglo~ ed or combined state.
This has the drawback of requiring an e~l,ensi~e extrusion step, wherein particular 15 eqllipm~nt and processing time is needed to extrude the particles together.

None ofthe above-cited doclll~l~llle discloses co--lpclu--ds, compositions or processes such as those described and claimed herein.

SUl~A[MA~RY OF TEE INVENTION

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 ~nh~n~ed adsorbent and/or ~nh~n~ed catalytic particle and/or for producing a 25 catalytic particle, comprising the steps of:
(a) removing an effective amount of air from a closed chamber cor~l ~il l;, ,p an adsorbent and/or catalytic particle, wherein the resultant cha",be~
pressure is less tham one atmosphere;
(b) raising the chamber pressure with an inert gas to at least one atmosph~re;
(c) cont~-,ting the particle with an energy beam of sllfficiçnt energy for a sufflcient time to thereby çnh~nce the adsorbent and/or catalytic gU~ t ~ht~l (RUIE 26) W 096/33013 PCTrUS96/OS303 properties ofthe particle and/or produce catalytic p,ul)e~lies in the particle.

The particle produced from this process can have room t~ ure catalytic capabilities 5 towards particular co.,~

The invention further provides a method for producing an Pnh~nced adsorbent and/or ~nh~,~ced catalytic particle and/or for producing a catalytic particle, comprising ;",pl~"l;,.g oxygen into an adso-l,elll and/or catalytic particle.
In yet another aspect, the invention relates to the particle made by the process of the invention.

In yet another aspect, the invention relates to an Pnh~nced adsorbent 15 and/or Pnh~nced catalytic particle and/or a catalytic particle colll~ ;ng an adsolbelll particle that has been treated to provide an excess of oxygen implanted at least on the surface ofthe particle to thereby form an f nh~llr,ed adsoll elll and/or çnh~nr.ed catalytic particle and/or a catalytic particle.

In yet another aspect, the invention relates to a binder for binding adsorbent and/or catalytic particles to produce an agglomerated particle cûlllplisillg colloidal ~lllmimlm oxide and an acid.

In yet another aspect, the invention relates to a method for binding adsorbent and/or catalytic particles, comprising the steps of:
(a) mixing colloidal ~lnmimlm oxide with the particles and an acid;
(b) ~gitiqting the mixture to homogeneity; and (c) heating the mixture for a s~lffici~nt time to cause cross-linking of the ~lllmimlm oxide in the mixture.

~UBSlllu~t~ (RUIE26) In yet another aspect, the invention relates to a method for reducing or g the amount of a CG~ from a liquid or gas stream co---p-;s;i g cont~ tin~ the particle ofthe invention with the co~llA~ l in the stream for a sufflcient time to reduce or ~olimin~tç the amount ofthe co..li....;l-~..l from the stream.
S
In yet another aspect, the invention relates to a method for adsorbing a co~ from a liquid or ga.s stream onto an adsorbent particle co..~.;s.ng cont~sting the particle of the invent;on ~,vith the co. ~ .l in the stream for a s~lfficiPnt time to adsorb the co,.l;...
In yet another aspect, the invention relates to a method for catalyzing the degradation of a hydrocarbon COlllpli~illg contacting the hydrocarbon with the palticle of the invention for a sllffi~iPnt time to catalyze the degradation of the hydrocarbon.

lS In yet another aspect, the invention relates to a method for reducing or e~ g the amount of a co~ ..l from a gas stream by catalysis co...~ il-p.contacting the particle ofthe invention with a gas stream col.l;.;..;l~p a c<,.~l~....;l-~.l comprising an oxide of nitrogen, an oxide of sulfur, carbon monoxidP~, or Illi~Lult;S
thereof for a sufficient time to reduce or Plimin~te the co,~ ";"~..1 amount.
In yet another aspect, the invention relates to an appal~LIls for producing an ~nh~nsed adsorbent and/or ,~nh~nced catalytic particle and/or for producing acatalytic particle comprising:
(a) chamber means for CG--I;~;ll;llg the particle in a closed system having an inlet gas port, an exit gas port, and a target plate, said chamber means being capable of ...~ g vacuum and positive pres~ul~;s, (b) means for providing an inert gas to the chamber means through the inlet gas port;
(c) means for withdrawing from the chal..~e. means an effective amount of ~ 30 the ambient air therein so as to create a vacuum within the chamber means; and SU~lllul~t!Sn~t~ (RULE26) W O96/33013 PCT~US96/05303 (d) means for providing an energy beam to the rh~mher means, said energy beam means outlet being targeted at the target plate.

In yet another aspect, the invention relates to a method for incl~;asing the 5 surface area of an adsorbent and/or catalytic particle, comprising the steps of (a) raising the chall-ber gauge Pl eS~UI'e of a closed rh~mhçrco~ the adsorbent and/or catalytic particle to at least 100 psi with an inert gas and (b) rapidly deco,.,l r essillg the chamber pressure to thereby increase the surface area of the particle.

In yet another aspect, the invention relates to a method for producing an Pnh~nced adsorbent and/or lonh~nced catalytic particle and/or for producing a catalytic particle, comprising the step of:
(a) cont~rting an adsorbent and/or catalytic particle with an energy beam of sufficient energy for a sufflcient time to thereby ~I~h~ e the adsoll,1ll1 and/or catalytic pl opel Lies of the particle and/or produce catalytic properties in the particle.

~rl(lition~l 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 ~tt~ined by means of the elements and colll~ alions particularly pointed out in the appended claims. It is to be understood that both the fol egoillg general description and 25 the following detailed description are eY~ ly and eypl~n~loly only and are not restrictive ofthe invention, as sl~imed The acco~ ying drawings, which are incol~ol~Led in and constitute a part of this specification, illustrate several embodiments of the invention and together 30 with the description, serve to explain the plinciples of the invention.

SU~lllu~tSJ~ (RULE2~) W O96/33013 PCTrUS96/05303 BRIEF DESCRIPTION OF ll~E DRAWINGS

Fig. 1 shows an appa~ us of one embodiment of the present invention for producing an çnh~n~ed adsorbent and/or e .-hAnced catalytic particle and~or for 5 producing a catalytic particle.

Fig. 2 is a graph showing the redwtion of NO using a particle ofthe invention.

Fig. 3 is a graph showing the red~lction of CO using a particle of the invention.

DESCRIPTION OF 1~E PREFERRED EMBODIMENTS

The present invention may be understood more readily by lere~ ce to the following detailed description of plerel-~d embod;...~ ofthe invention and the F~mrles included therein and to the Figures and their previous and following description.

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 partir.,ular embodim~ntc only and is not intended to be limitin~
It must be noted that, as used in the spe~ific~tion and the appended daims, the singular forms "a," "an" and "the" include plural rc~elell~s unless the context clearly dictates otherwise.

In this specific~tion and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following me~ning~

SUB~ t SHEE~ ~RULE 26) W O96/33013 PCTrUS96/05303 "Optional" or "optionally" means that the subsequently desc"bed event or cirr~ nce may or may not occur, and that the description inrllldes in~t~nççs where said event or circ~m~tAnce occurs and in~tAnCÇS where it does not.

The term "particle" as used herein is used illLe~rl-AI~grAl-ly throughout to mean a particle in the singular sense or a co",l~il,aLion of smaller particles that are grouped together into a larger particle, such as an ~lomçration of particles.

The term "ppm" refers to parts per million and the term "ppb" refers to 10 parts per billion. GPM is gallons per minute.

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 f.nhAnred adsorbent and/or enhAnçed catalytic particle and/or for producing a15 catalytic particle, comprising the steps of:
(a) removing an G~G~iLi~, amount of air from a closed cha-"be, co... ~ an adsorbent and/or catalytic particle, wl~elein the resultant ~h~.. l.~.
p, G~Sul e is less than one atmosphere;
(b) raising the cha",ber plG~:~UlG with an inert gas to at least one atmosphere;(c) contActing the particle with an energy beam of sllffir.irnt energy for a sufficient time to thereby f l~hAnçe the adso,l,t;nL and/or catalytic properties of the particle and/or produce catalytic properties in the particle.

25 The particle produced from this process can have room ttlll~GI~lu~G catalytic capabilities tov~cuds particular co.,li..nil-~

The invention further provides a method for producing an e-nh~nced adsorbent and/or çnh~nr,ed catalytic particle and/or for producing a catalytic particle, 30 CO",~,isi,lg implanting oxygen into an adsorbent and/or catalytic particle.

S~IB~ Ult~d~l (RULE26) W096/33013 PCT/US96tO5303 _ 9 _ In yet another aspect~ the invention relates to the particle made by tlhe process of the invention.

In yet another aspect~ the invention relates to an ~nh~n~ed adsorberlt 5 and/or P.nh~nced catalytic particle and/or a catalytic particle complis-ng an adso-bt~
particle that has been treated to provide an excess of oxygen ;...p~ ed at least on the surface of the particle to thereby forrn an ~nh~nt~.ed adsorbent and/or ~nh~nced catalytic particle and/or a catalytic particle.

In yet another aspect, the invention relates to a binder for binding adsorbent and/or catalytic particles to produce an agglomerated particle colll~li~ill;g colloidal ~ n;.. ,, oxide and an acid.

In yet another aspect, the invention relates to a method for binding 15 adsorbent and/or catalytic particles, co---~ ing the steps of:
(a) mixing colloid~l ~h~mimlm oxide with the particles and an acid;
(b) ~jt~tin~ the mixture to homogeneity; and (c) heating the mixt~re for a s -ffi~;~nt time to cause cross-linking of the mim~m oxide in the mixture.
In yet another aspect, the invention relates to a method for reducing or eli. . .i n~ ;,-g the amount of a CO~ from a liquid or gas stream co---~-ising cont~cting the particle ofthe invention with the CO."n...;,~ in the stream for as ~ffirient time to reduce or elin-in~te the amount ofthe co,~ "~ from the stream.
In yet another aspec~, the invention relates to a method for adsorbing a co"~n...;,~"l from a liquid or gas stream onto an adsorbent particle co---~ i--gcont~cting the particle of the invention with the co"l n~ in the stream for a s-lffir,içnt time to adsorb the coll~nlllin~

SUBSrrTUlE SHEET (RULE 26 WO96/33013 PCTrUS96/0~303 In yet another aspect, the invention relates to a method for catalyzing the degradation of a hydrocarbon co,-.l" ;~ g cont~cting the hydrocarbon with the particle of the invention for a sllffici~nt time to catalyze the degradation of the hydrocarbon.

In yet another aspect, the invention relates to a method for reducing or eli" ,i l ,h ~ g the amount of a co"l A " ,; ~ ,l from a gas stream by catalysis compricing cont~cting the particle ofthe invention with a gas stream ÇOI,Ih;,l;llP a COIIIh~
comprising an oxide of nitrogen, an oxide of sulfur, carbon monoxitle, or n~Lul~s thereoffor a s lffi~ i~.nt time to reduce or ~limin~te the co"lh".;.-~..l amount.
In yet another aspect, the invention relates to an apparatus for producing an ~nh~nced adsorbent and/or ~nh~n~ed catalytic particle and/or for producing a catalytic particle col-lpli~ g.
(a) chamber means for col~lh;~ g the particle in a closed system having an inlet gas port, an exit gas port, and a target plate, said cl ~llb~l means being capable of ~h;~llh;~ g vacuum and positive ple~ul~ ;"
(b) means for providing an inert gas to the challlber means through the inlet gas port;
(c) means for withdrawing from the chamber means an effective amount of the ~mbient air therein so as to create a vacuum within the ch~n~.
means; and (d) means for providing an energy beam to the chall,ber means, said energy beam means outlet being talg~:Led at the target plate.

In yet another aspect, the invention relates to a method for inc.t;a~i,lg the surface area of an adsorbent and/or catalytic particle, comprising the steps of (a) raising the chamber gauge ples~ule of a closed chamber co"~ ;l-g the adsorbent and/or catalytic particle to at least 100 psi with an inert gas and 30 (b) rapidly decolllpr~s~illg the chamber pres~ul~ to thereby increase the surface area of the particle.

tTUrE SHEET (RUl~ 26) _ W O96/33013 PCTrUS96/05303 In yet another aspect, the invention relates to a method for producing an PnhAn~ed adsorbent and/or çnhAnced catalytic particle and/or for producing a catalytic particle, comprising the step of:
(a) cont~ctin~ an adsorbent and/or catalytic particle with an energy beam of ~lffi~j~nt energy for a s~ffi~ient time to thereby Pnh~n~e the adsorbent and/or catalytic pl~pGI Lies of the particle and/or produce catalytic plU~ ies in the particle.

By PnhAnced adsorbe~t and/or çnhAnced catalytic particle, it is int-ontled that the particles of this invention have improved adsorbent and/or improved catalytic rop~l ~ies over prior art adsorbent and/or catalytic particles. Also, by producing a catalytic particle, it is inten-led thlat some particles of the instant invention have catalytic prope.lies for catalyzing the coll~ ;on of particular COI~IAI~;n~A~ into other forms, wheleas the same particles not treated by the process ofthe present invention possess no catalytic plul)el Lies at least for th~ose particular co-~l 'Al~ A~

F.nhAn-~ed adsorptive PIOPGI ~ies is int~n-led to include both ion capture and ion ~ .A I1ge I l leChA ~ . Ion capture refers to the ability of the particle to bond to other atoms due to the ionic nature ofthe particle. Ion l ~cl-A~ge is well known in the art and refers to ions being ill~ .hA l~ged from one substance to another. Adsorption is a term well known in the art and should be dictin~li~hpd from absol~lion.

In the particle of this ;nvention, typically any particle that initially has some adsorbent and/or catalytic p-Opel Lies can be used. For PY~Amrle, activated calbon and oxide particles can be oxygen implanted by the process of the present invention.

For oxide particles, oxides of metals or oxides of non-metals, such as silicon or ge- ".~ , are pl t;re~ l ed. Even more pl t;r~ d are oxides of transition metals, oxides of metals of Growp I~[ (B, Al, Ga, In, Tl) and IA (Li, Na, K, Rb, Cs, Fr) 30 of the periodic table, and oxides of silicon. Particularly p- ~rc;c:d oxides include -Alllmin~lm oxide (Al203), silicon dioxide (SiO2), mAn~nese dioxide (MnO2), copper Ul~ SHEEr (RULE26) CA 02227428 l997-l0-20 W O96/33013 PCT~US96/05303 oxide (CuO), iron oxide black (Fe3O4), iron oxide red (ferric oxide or Fe2O3), zinc oxide (ZnO), zirconium oxide (ZrO2), v~n~ m p~ntQ~ide (V205), and tit~nillm dioxide (TiO2).

S In one embodiment, the particle comprises ~lllmin~ oxide that has been pre-treated by a full calcination process. C~lrined ~lllminllm 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 c~lcin~d ~lllminllm oxide particles are well known in the art as disclosed in, e.g., Physical and Chemical Aspects of Adsorbents and Cafalysts, ed. Linsen et al., ~r.~d~mic Press (1970), which isincorporated by lerelence herein. In one embodiment, the Bayer process can be used to make ~lllminllm oxide precursors. Also, pre-calcined ~lllmimlm oxide, that is, the ~lllmimlm oxide precursor (Al(OH)3), and calcined ~lllmin~lm oxide are readily commercially available. C~l~ined Rlnminllm oxide can be used in this dried, activated form or can be used in a partially or near fully deactivated form by allowing water to be adsorbed onto the surface ofthe particle. However, it is p,G~l~ble to r..;l~;i..;,~ the deactivation to l~-AX;~ 9 the adsorbent capability.

In a ~lere"ed embodiment, the ~lllmimlm oxide has been produced by 20 c~ ning at a particle temperature of from 400~C to 700~C. These p,ere"t;d ~lllmimlm oxide particles are l~l eft;l ~bly in the gamma, chi-rho, or eta forms and have a pore size of from 3.5 nm to 35 nm di~meter and a BET surface area of from 120 to 350 m2/g.

For activated carbon, any of the activated carbons useful in the adsorbent 25 art can be used. Preferably coal based carbon or coconut based carbon are used.
Generally, coal based carbon can be used to rçm~ te aqueous co, .l ;. ,~ c whilecoconut based carbon can be used to rlom~ te airborne or gaseous co"~ ,;"~
Plere,~bly, the activated carbon is less than 20 microns in size for ease of mixing and extrusion.

SU~lllult~h~to (RU~E26) -WO96/33013 PCT~US96/053~3 The particle of the invention can be used alone, in co,l,~ aLion with identic~l or di~ele~lL type compositiom particles plepa.ed by the p.ocesscs ofthe invention, and/or in colllbilla~ion with other adsorbent or catalytic particles known in the art. The particles can be combined in a physical mixture or agglolllel~LLed using S techniques known in the art or d;sclosed herein. In a plcrélled embodiment, d;~ercllL
composition type particles are combined by a~glomrration to form a mllltifilnctiona composite particle. In this embodiment, particles can be used to achieve mllltiple fimr.tion~ simlllt~neously, such as by removing multiple co~ , by taking advantage of the individual effects from each of the types of particles. Co-particles that 10 are preferably used in this invention include all particles previously disclosed and zeolite.

In one embodiment, the composite particle col,l~lises ~ ",;"~". oxide and a second particle oftit~ni--m dioxide, copper oxide, v~n~tli-lm pentoxide, silicon 15 dioxidr~ g~l-ese dioxide, iron oxide, zinc oxide, activated carbon, or zeolite. In another embodim~nt, the composite particle colll~,ises ~lllmimlm oxide and activated carbon. In another embodiment, the particle co",~u,ises activated carbon (coal-based?, activated carbon (coconut-based), silicon dioxide, and ~lllminllm oxide. In a pleîellèd embodiment, this particle is used to le~.,e~liA~e aqueous co"l~",;..~lion In one20 embodiment, this particle of coal-based activated carbon, coconut-based activated carbon, silicon dioxide, and alllrninllm oxide is used to rome~ te aqueous co~lA~
such as 1,2-dibromo-3-chlol opl opane (DBCP), radon, and heavy metals, from a co,~lA,n;,~ted water source.

The particles of this invention can be subjected to other surface tre~tmrnt~ prior to or after being treated by the process of the present invention. The particles of the invention can be pretreated by processes known in the art to illlplo~,e their adsorptive capability, such, as by r,~lr.in~tion ~lrin~tion refers to heating a solid to a temperature below its melting point to alter the crystal structure to a particular - 30 form. The calcinated particle can be dried or ,~,~."~ ed in dry form cle~Lll~, an activated particle or, if water is absorbed on the particle, the particle can be partially or ult!;llE~ULE26) CA 02227428 l997-l0-20 WO96/33013 PCTrUS96/05303 near fully deactivated. In one embodiment, the particles of this invention can be in dry, slurry, or gel form. The particle size can vary depen.lillg on the end use, rangin8 in sizes known in the art, such as collQi(l~l, microscopic, or macloscopic. Preferably, the particles prior to agglomeration are less than 20 microns in size for ease of mixing and 5 extrusion.

Binders for binding the individual particles to form an agglomel~Led particle are known in the art or are described herein. In a ~l~relled embodiment, the binder can also act as an adsorbent and/or a catalyst. A plerell~d binder for the 10 agglomerated particle is colloidal alumina or colloidal silica. At approx;,.~ o,ly 450~C, the colloidal ~ min~ goes through a tran~rullll~Lion stage and cross-links with itself.
Colloidal silica cross-links with itself if it is s -ffiçiently dried to remove water.
Preferably, from about Z0 wt. % to about 99% of the total mixture is colloidal ahlmin~
or colloidal silica to provide the nece~ry cros~ ki~-g during heating to bind the 15 agglomerated particle into a water-re~ ~lL particle. The particle can then w; exposure to all types of water for an ~oytentled time and not degrade.

In one embodiment, the agglomerated particle is made by mixing colloidal ~lllmin~ with the adsorbent particles. Typically, from about 2p% to about 99%
20 by weight ofthe mixture is colloidal alllmin~ The particle mixture is then mixed with an acid solution such as, for example, nitric, sulfuric, hydrochloric, boric, acetic, formic, phosphoric, and ., i~Lu. es thereof. In one embodiment the acid is 5% nitric acid solution. The colloidal ~lllmin~ adsorbent particles, and acid solution are thoroughly mixed so as to create a homogenous blend of all elem~nts Then addition~l acid sol~ltion 25 is added and further mixing is performed until the mixture reaches a suitable con~i~ten(cy for agglomeration. After agglomeration is complete, the agglomerated particles are heated to at least 450~C to cause the colloidal alumin~ cro~clinkin~ to occur.

Sources and/or methods of making the starting materials for the various 30 adsorbent particles of the present invention are readily available and are well-known to those of oldill~y skill in the art.

SUBSII~u~hk~l ~RULE26~

W O96/33013 PCTÇUS96/05303 For an explanation of the process used to make a particle of one embodiment ofthis invention, reièrence is made to Figure 1. The app~ s ofthis embodiment is dçcign~te(l generally as 10 The particulate m~tPri~l or target medi~ 20 to be treated is placed in a chamber 11 on ungrounded target plate 22. In one - S embodiment, the target plate can be rotated to provide more efficient ~ of the particle by the energy bearn. Chamber 11 is preferably made of a dielectric material Chamber 11 is sealed by a col..~l es~ion plate latched door 12 that has the ability to wi~ rl high co...~.es~ion ratios both in the positive as well as negative pressures Pressure is ~--o- ilo-t;d with pressure gauge 18. Vacuum con~lition~ are created in the 10 chamber using vacuum pump 19 to evacuate an effective amount of air initiallyco~ ed in the cl.~".her. Air can be dt~ ,.-Lal to the oxygen i---pl~-~a~ion step in that it reduces the ~fficiçncy of the energy beam's affect on the particle Evacu~tin~ an effective amount of air is intçntled to mean that enough air is removed so that the energy beam has the ability to çnh~nce the adsorbent and/or catalytic plop~llies and/or produce 15 catalytic plu~Jel Lies in the particle. Typically, vacuum pump 19 is used to evacuate as much air as possible from çh~mherll to ~nX;~ ; the energy beam's efficiency an~ to allow a beam of lower energy to be used The ch~--ber is brought up to a pre~ul~ of at least atmospheric pressure using an inert gas from cylinder 13 through a high p.~s~ure injector 17. In one embodiment, the gauge pressure (pressure above atmospheric) is 20 from 1 to 5,000 psi Typically, the gauge p-e~su-e can be at least about 20 psi to prevent arcing.

The inert gas is typically any gas that is inert to ç~Pmic~lly reacting with and degrading the adsorbent palticle, and yet, does not impede the energy beam's25 effectiveness in implanting the oxygen. Typical inert gases include the noble gases, such as helium, neon, argon, krypton, xenon, and radon The energy source is targeted at the particle co~ ined in the ch~--ber through an energy injector 1~ located at the end ofthe energy source 14 The energy - 30 source can be of any high energy that can force oxygen into the particle andJor add excess charge to the particle Typically, the energy source is an ion m~çhin~ which SUBSTITUTE SHEET (RULE 26) WO96/33013 PCTrUS96/0~303 CQnCe~ leS an ion or electron beam, such as a broad beam ion source or a wide beam photoinni7tor. In a specific embodiment, the energy source can be a broad beam ion source, m~nnf~ctllred by Commonwealth, ~c~ , Virginia, U.S.A. having a n output of 25 eV. The energy source 14, utilizes a power supply 21. In a 5 specific embodiment, the power supply can be a Commonwealth IBS-250 high voltage power supply rated up to 1500V with remote operation c~p~hiliti~s A~ itio~lly, the energy beam causes the inert gas to become ionized. The charge introduced into the chamber is at a level s~lfficiçnt to enh~nre the adsorbent and/or catalytic properties of the particle and/or produce catalytic p, O~l Lies in the particle. In one embo-liment, an 10 cle~iLlon beam of 15 to 20 eV was used, although a smaller or larger amount of energy can be used. Once the proper charge has been ~tt~ined for a sllfficient time, the energy source is turned off. This sufficient time can be very short, on the order of less than a second to about 10 secon~ls, although a longer time is not d~ t&l. Then, the cl,~"l)el pressure is deco,n~ sed via a release valve 16.
Not wishing to be bound by theory, it is theorized that the energy beam causes monoatomic oxygen present on the surface of the particle to be pushed below the surface of the particle, which then becomes tightly bound to the internal structure of the particle. For crystalline particles, the oxygen beco,l,es tightly bound within the crystal 20 lattice. The monoatomic oxygen originates from oxygen that is on the outer surface of the crystal lattice of the particle or from residual water or air on the surface of the particle. This increases the adsolbenl and/or catalytic characteristics of the particle and can create catalytic propt;,L,es, inçl~lrlin~ room tt;""~ L-Ire catalytic capabilities, in the particle. It is additionally ~l,eoliGed that the advantageous p,~pelLies ofthe particle of 25 this invention result from the energy beam adding an electrical charge or in~ ased electrical charge to the particle.

In another embodiment, in the energy beam proces above, after the air has been removed from the chamber, inert gas is added so that the chamber pressure is 30 brought up to a high pressure. Typically, the gauge pressure can be from about at least 100 psi, more p,~lably at least 1,000 psi, even more ple~l~bly at least 5,000 psi.

Sl~a~a~J~k~t~ (RULE26) W O96133013 PCTrUS96/05303 Even higher p. es~u- GS can be used if the cllalllbel 15 of a high enough pressure rating.
The high pressure or co...~.ession is ~ ed for a sllfficient time to increase the density of the particle. Residual air is bled from the vessel, thereby removing any residual air from a puffed up parl:icle~ until a consla.,~ pressure can be .. ~;"l~ d S Typically, about ten minutes of hligh pressure is sl lffic i~nt After the energy source has been introduced for a sllffiri~nt time in the chamber as described above the energy source is turned off and then the chamber pressure is rapidly decolnp, ~ssed via release valve 16. By rapidly it is plerG ~bly meant about 3 seconds. This increases the surface area of the particle.
Not wishing to be bolmd by theory it is tl~o, ;7Pd that as the prGs~ulG
from the chambel is rapidly released, the co"~e"~s ofthe chamber expand ~imlllt~nçously but at di~GIGllL rates of c ~ ;on. The charged inert gas PYp~n~l~ at a much faster rate than that of the particulate matter due to the density differences between the two 15 subsl~lces. Due to this PYp~n~ion rate diLrGlGllce the charged inert gas travels rapidly and penetrates or explodes into and ~hrough the particles. This rapid pel,~ ion alters the pore structure and increases the amount of pores of the particle. The surface area of the particle is thereby greatly hlc.Gased hl.;,~iasi"g the overall adsorption capability of the particle. Depelldi..g on the particle employed the BET surface area can be incl eased 20 at least 1% more preferably at least 5% even more preferably at least 10% even rnore preferably at least 20%, even more plerGI~bly at least 30%. The lower density particles such as activated carbon, can achieve a greater inclGase in surface area.

The ch~--ber p-essu.~ and the energy level can be varied to produce 25 di~ren~ effects to meet the par~icular physical and ch~mic~l req~,i,e",~"~s for the specific particle end use. Varying the pl es~u- G and energy level p~ ~lllGLG. ~ can alter the ability ofthe particle to adsorb a particular co"l;l",;" ~"1 -In another embodiment of this invention the surface area ~nh~n~em~nt - 30 aspect of the process can be practiced alone without the energy beam aspect. In this embodiment, the inert gas only needs to be inert to the particle and does not have to be S~ u~t ~hstl tR~l,E 2B~

WO96/33013 PCTrUS96/0~303 inert to the effects of the energy beam. Thus, gases such as air and CO2 can also be used in the this embodiment.

In another embodiment, the energy beam aspect can be practiced alone 5 without the surface area ~nh~ncçmPnt aspect. In this embodiment, the energy beam is targeted directly at the particle to implant oxygen within the particle. This can be done in the batch process described above or a semi-batch or contin--o -~ process. In a semi-batch process, particles are ~--tom~tic~lly moved into the ch~mhçr where they are treated and ~utom~tic~lly removed from the ch~~ er. In a contin~o~ process, in one 10 embodiment, the particles are provided on a collve:yor belt system. Air is displaced from the area around the particles by inert gas to provide a viable path for the energy beam, which is set up along side or overhead of the conveyer belt system. The energy beam is either continuously on or is turned on as the particles reach a specific point along the conveyer belt system. In a variation of the embodiments of this invention, the air 15 removal and repl~cPm~nt with inert gas steps in the batch or semi-batch processes and the air tli~pl~cP~mpnt by inert gas step in the continuous process can be avoided by using an .,,~LIel.lely high level of energy source, such that, the air does not impede the oxygen from penetrating the surface of the particle. In another embodiment of a contim~o~s process, the particles are filtered through a mesh screen sieve, which has been 20 subst~nti~lly ionized to cause the oxygen on the particle to pen~ e the particle.

The particles of this invention are characterized by having an incl eased level of oxygen at least on the surface of the particle. This increased level of oxygen is higher than the total of the stoichiometric amount of oxygen eYpected in the particle and 25 that found as residual oxygen on the surface of the particle. The oxygen impl~nted particle has at least 1.1 times the oxygen atom per cent to non-oxygen atom per cent ratio at its surface colll~t;d to the initial non-oxygen ;",pl,."led particle, vvhelein the surface characterization is determined by an x-ray photoelectron spectroscopy (XPS or ESCA) specLIullleLer, a device well known to those of skill in the art. Even more 30 plerel~bly, the particle has at least a 1.5 fold increase in oxygen ratio, even more preferably the particle has at least a 2 fold increase in oxygen ratio, even more SUB~ ttl (RUlE26~

WO96/33013 PCTrUS96/05303 preferably, at least a 4 fold increase in oxygen ratio, even more preferably at least a 6 fold increase in oxygen ratio.

The particle of this i~vention can be used in any adsorption and/or S catalytic app~ tion known to those of ol.lin~y skill in the art to achieve supclior results over prior art particles. ~ ition~lly, the particle of the invention can be used in various adsorption and/or catalytic applications never before co.~le~ .lated in the art. In one embo~lim~1lt~ the particle is used for environm~nt~l le~"e~ ;Qn applications. In this embo-lim~nt the particle can be used to remove c~."l~.";~-~..le such as heavy metals, 10 organics, in~h1din~ for example but not limited to, chlorinated organics and volatile organics, inorganics, or .",~lU,t;s thereof. Specific eY~mples of ccs..l~...;l-~..l~ include, but are not limited to, acetone, microbials, ~.. oni~ benzcne, carbon monoYide, chlorine, diox~ne, ethanol, ethylene, formaldehyde, hydrogen cyanide, hydrogen sulfide, nol, methyl ethyl ketone, methylene chloride, nitrogen oxides, propylene, styrene, 15 sulfur ~io~ide~ toluene, vinyl chloride, arsenic, lead, iron, phosphates, s~l~nil-m c~-lmi--m, uranium, ph~toni-lm radon, 1,2-dibromo-3-chloloplùpalle (DBCP), chromium, tobacco smoke, and cooking fumes. The particle of this invention can r~me~ te individual co"l~""~ or multiple co"l~",;~-~"l~ from a single source.

Foren~ ulllll~ ,,e~ napplications,typically,particlesofthe invention are placed in a colllail]lel, such as a filtration unit. The co"~ ";l,~led stream enters the col,~ er at one end, contacts the particles within the co~ er~ and the purified stream exits through another end of the con~ailler. The flow rate of the co"l ~ ,-l stream and the amount of particle m~teri~l needed can be determined by one of skill in the art with routine expe, ;" ,~ l ;o~ by dt:lt;""il~ing the capacity needed.
The particles contact the co,.l~ within the stream and bond to and remove the co"li1",i~ n from the stream. The particles can also ~limin~te certain co,,l~ bycatalyzing the conversion of the co~ into other components. Typically, in the adsorption application, the particles become saturated with co~ ,lc over a period - 30 of time, and the particles must be removed from the container and replaced with fresh particles. The co~ l stream can be a gas, such as air, or liquid, such as water.

SUBSl~lU~ t~l (RULE26) W O96/33013 PCTrUS96/05303 In the adsorption application, the particle of this invention bonds with the co,~A~ so that the particle and co~ n~ A~.I are tightly bound. This bonding makes it difficult to remove the coi~",il-A~.~ from the particle, allowing the waste product to either be disposed of into any public landfill or used as a raw material in the building S block mAm-f~ctl-ring industry. Measu,el"ents of CQ.I~ adsorbed on the particles of this invention using a Toxic Chemical TeA-.hAte Permit (TCLP) test known to those of skill in the art showed that there was a bond at least as strong as a covalent bond between the particles of this invention and the col ,l ~ ~ ";, ~, ,I s The particles of this invention have superior ability to adsorb co,.l~ "l~ due to ~nh~nf~ed physical and çl.~".;çAl prc.pe,lies ofthe particle. The particles of this invention can adsorb a larger amount of adso,l,aLe per unit volume or weight of adsorbent particles than a non-Pnh~nced particle. The particle of thisinvention surprisingly removes conl~,,inAlll~ in various streams at both high and low 15 conc~ ,l, aLions of CG- ll ~ . . .i l~zi. .l ': Also, the particles of this invention can reduce the conce"~,~lion of co~ A~ or adsorbate material in a stream to a lower absolute value than is possible with a non-çnh~nced particle. In particular embo-lim~nts, the particles ofthis invention can reduce the co..l~ .l conce"L,~Lion in a stream to below detectAble levels, never before achievable with prior art particles.
The particles of this invention can also have a newly added catalytic property. Specifically, the increased oxygen content in the particle matrix allows the particle to act as a catalyst. For example, the particle has the ability to catalyze the break down of hydrocarbon compounds and has the ability to catalyze the conversion of 25 CO, SOx, or NOX into other components, even at low heat or room t~lllpel~ules.

Particular end uses co, ,l ~ ,rl~ted by this invention include, but are not limited to, reducing or ~limin~ting col-lA~ c for particular applications, such as waste water ~,e~l~"~"l facilities, sewage f~ lities~ mllniçirAl water purification fA~ilitif-c, 30 in-home water purification systems, smoke stack ~m~lçnt~, vehicle exhaust ~ ents, engine or motor çffl~lçnt~, home or building air purification systems, home radon SUB~ u~ SHEEr (RUIE 26) WO96/33013 PCTrUS96/05303 lf~"-e~ tions, landfill le~ch~te~, m~mlf~ctllring facility rh~mic~l waste .offlllPnt~ and the like.
-Prior art adsorbents, such as activated carbon, when sprayed with anti-microbials, tend to lose their adsorbent properties. Conversely, the increased adsolbt:-"
properties allow the particles of the present invention to be sprayed with anti-microbials while still, ~ g the particle's adsorbent prope, lies. Moreover, unlike prior art particles, contact with water doex not deactivate the adsorption capability of the inventive particles.
Expel illlt;lllal The following ~y~mrles are put forth so as to provide those of o,dh~y skill in the art with a complete disclosure and description of how the co",~ou,lds claimed herein are made and evaluated, and are intçntled to be purely ~ .y ofthe invention and are not intçnded to limit the scope of what the h~venlo~ 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 accou"Led for. Unless in~1ic~ted otherwise, parts are parts by weight, temperature is in ~C or is at or near room te"")e,~lu,c; and pressure is at or near ~tmospheric.

Example 1.

Various particles were made in accordance with the procedures of this invention as follows. The procedures used to prepare the particle dçcign~ted as la in Table 1 below, having a composition of 60% A12O3, 20% carbon, 15% m~n~nese dioxide and 5% copper oxide, is ~Yçmplified The ~lllmin~ utilized was a gamma c~l-.ined (550~C) ~ min~ derived from a high density, low porositv pseudoboehmite min~ or ~ min~ gel. The alumina was pretreated by c~l~ining to 550~ C to reach the -30 desired gamma crystalline structure. The carbon utilized in this particle was a coconut based carbon, design~ted as Pol~mesian coconut based carbon purchased from Calgon SU~IllultSntltl I~RUIE26) W O96/33013 PCTrUS96/05303 Carbon Corporation. Due to the use of coconut shells in the m~mlf~ctllre of this carbon, there exists a very large surface area as well as micro-pores which are useful for "~ing co~ in a gas stream. The four individual particle types were mixed together in their appl op, iate weight per cents accor.l;"g to the dry weight. They were S mixed together into a homogenous dry mixture. An acid sollltion of 20parts by weight of 80% nitric acid was added to 80 parts by weight of water. The acid solution was added to the dry particle mixture slowly until the mixture obtained a moist pasty co~ lç~ y. This con~i~tçncy allowed the mixture to be extruded into the desired forrn.
The mixture was extruded using a LCI model BTGa9 laboratory extruder. After the 10 mixture was extruded, the extrudate was chopped up into app,."~i",alely one-si~ee"l to one-eighth inch particles and then was dried at a temperature of at least 450~ C to cross-link the ~ mimlm oxide. The particles were placed in a vacuumlpressure vessel ch~"ber on an ung~oullded target plate. The door to the ch~"ber was secured, and air was pumped out of the ch~nbel down to a negative p,~.sa..le of two militorrs. Upon 15 reaching this pressure, argon gas was allowed to bleed into the chamber and reach an internal gauge plesaur e of about 20 pSi. Upon reaching this pressure, the energy beam source was activated to 15 to 20 eV and was applied to the particle on the target area.
A Co"""o"wt;alth broad beam ion source was used. Tl~ .e.~l times for the particles vary according to the amount and density of material on the target. For this example, a 20 volume of 50 grams of material was used and a tre~tm~nt time of ten seconds was used.
The ~ times also vary according to the output power from the energy beam source and the internal pressure in the chamber. After ten seconds, the ion source was turned off and the chamber was evacuated to atmospheric pressure. The sample wasthen removed from the cha",be,.
Particles lb through lac were similarly made in accordance with the above-described example for 1 a except that the particular compositions were as set forth in Table 1. Also, the carbon utilized for aqueous particle de~i n~tions lv and lw was a coal based carbon. This coal based carbon was purchased from Calgon Carbon 30 Corporation as WHP grade carbon. The particular alumina utilized in particles lb through lac was the sarne as described above for particle la, a gamma s~ ined ~ nnin~

SUB~ lllt~t~l (RUlE26) The other components listed below in Table 1 are well known and are readily available to one of skill in the art.
-~Each of the particle's composition made in accordance with the 5 procedures ofthis invention described above and the co.~ it was tested with inExamples 2 and 3 are listed below in Table 1. The same particle dç~ tion system is used in Tables ~-3.

S~ a~ UlE 2~

PARTICLE COMPOSlTIONI CONTAMINANTS
DESIGNATION (weight %) AIRBORNE AQUEOUS
I a 60% Al2O3,20% Carbon,15% Acetone MnO2, 5% CuO
Ib 100% Al2O3 Ammonia Ic 50% Al203,40% Carbon,10% Beuzene sio2 Id 40% Al203,30% V205,20% Carbon M~.. tlf MnO2,10% TiO2 le 100% Al2O3 Chlorine lf 100 % Al2O3 1,4-Dioxane I g 100% Al2O3 Ethanol Ih 100% Al203 Fc, ---al~h~
li 40% Al2O3,30% MnO2,20% Hydrogen Cyanide V2O5,5% Zeolite,5% Fe2O3 Ij 30% Al203, 50% MnO2,5% Hydrogen Sulfide Carbon,5% SiO2,10% ZnO
Ik 90% Al203,10% Carbon M~t~ ,1 11 100% Al2O3Methyl Ethyl Ketone lm 40% Al203,20% MnO2, 10% M_ll.jl~,.. ~, Chloride CuO,30% V2O5 In 40% Al2O3,30% V2Os.20% Nitrogen Oxides MnO2.10% TiO2 lo 30% Al203,70% Carbon Plu~ e Ip 30% Al2O3, 70% Carbon Styrene 1 q 100% Al2O3 Sulfilr Dioxide Ir 40% Al2O3,30% MnO2,30% Toluene Carbon ls 30% Al203,70% Carbon Vinyl Chloride lt 100% Al2O3 Arsenic lu 100% Al2O3 C- ' lv 40% Al203,40% Carbon,20% Chlorine sio2 SUBST~TUTE SHEET (RULE 20~

W O96/33013 PCTrUS96/05303 PARIICLE COMPOSrrIONl CONTAMDNAN~
DESIGNAIION (wei~t%) AnRBOFU~E AQUEOUS
Iw 40% A1203, 40% Carbon,20% DBCP
sio2 Ix 100% A1203 Iron 00% A12~3 Lead Iz 100% A1203 1aa 40% A1203, 40% C~bon,20% Radon sio2 lab 100% A1203 Seleniurï
lac 100% A1203 Ural~ium Activated carbon coconut based was used for the airborne co..li..,.;..~,.l~ and for laa (radon) and &_liv~led carbon coal based was used for ~queous co.~ lv and lw.

E;sample 2.

The particles made in F.~mple 1 were tested for their ability for removal 10 of various components from air. The tests for the a;ll,ullle co..l~ as sulll~ ed in Table 2 below were performed as follows. The co..l,....;..~ source used was either solvent vapor or an offthe shelf bottled gas mixture. Solvent vapor was mixed with humid air by injecting into the systern with a syringe pump. A gas bottle with a needle valve and a flow meter, either a rotarneter or a mass flow meter controller, was used to blend the gas bottle effluent with the humid air. Humid air at 30% relative humidity and 25~C was mixed with either the solvent vapor or gas stream. The humid air was ~enelaled by a flow-ttlll~ L.Ire-humidity control module which controlled temperature, relative humidity and the flow rate of the humid air. The concel~ lion of the airborne co..~ l in the humid air was then Illea~u,ed by an infrared analyzer.
After the influent infrared analysis, the sarnple entered a sarnple holder. The sample holder was a three-inch tli~meter test vessel, which held a 200 gm amount of particle sample in place using a fritted disk. After passing through the particles, the concellll~lion ofthe co~ ...in~ in the effluent exited the sample holder. The SUBSrtTlrrE SHEET (RULE 26~

W O96/33013 PCTrUS96/05303 co~ P .l . ~lion of the CQ~I A ~ ~ ~' 1~- ~1 in the effluent side of the particle sample holder was also analyzed with an infrared analyzer. The test time was ten mim-tçs Percent removal was c~lcc~ ted as (initial coi.l~",;,~A~.I concentration minus effluent co,~ h~
collcenL-~lion) divided by initial col,l~,..;l-~,l conce..L.~lion.
S
The results are set forth in Table 2 below.

INITIAL
PARTICLE AIRBORNE CONTAMINANT PERCENT El.OW
DESIGNATIONCONTAMINANT CONCENTRATION REMOVAL RATE~
(ppm) la Acetone 750 100 40 Ptlmin.
Ib Ammonia 50 100 40 ~/min.
Ic Benzene 50 100 40 R/min.
Id CarbonM nr~Yi~l~ 10000 100 40ft/min.
le Chlorine 34 100 40 ~/min.
If 1,4-Dioxane 50 100 40 ft/min.
Ig Ethanol 1000 100 40 ft/min.
Ih Ful.. lald~,h~ 10 100 40 ft/min.
Ii Hydrogen Cyanide 20 100 40 ft/min.
Ij Hydrogen Sulfide 20 100 40 ft/min.
Ik Methanol 200 100 40 ft/min.
Il Methyl Ethyl 1000 100 40 ft/min.
Ketone ImM~,llljl~,.-~, chloride 50 100 40 ft/min.
In Nitrogen Oxides 100 100 40 ~/min.
Io Flu~ , 700 100 40 flL/min.
Ip Styrene 50 100 40 ft/min.
Iq SulfilrDioxide 20 100 40ft/min.
Ir Toluene 100 100 40 ~/min.
Is Vinyl Chloride 20 100 40 ftlmin.
40 flL/min velocity was 55.5 I/min volumetric flow.

SUESll~u~ tl (RULE26~
-WO96/33013 PCTrUS96/053a3 In Table 2 above, for the formaldehyde test using particle lh, formaldehyde was not detected on the particle after the test was completed and, as shown in Table 2, no formaldeh~de was detected in the ef~luent stream. This particle lh acts as a catalyst towards formaldehyde and breaks down the formaldehyde into what is 5 believed to be CO2 and water, e~en at room t~l~lpel~L~Ire. This was further evidenced by a separate test in which it was shown that the formaldehyde was removed from thesystem over a subst~nt~ y longer period oftime than can be ~ ;..ed if the particle acted only as an adsorbent.

As can also be seen from the above Table 2, carbon monoxide and nitrogen oxides were not detected in the effluent system. Because these two components do not normally adsorb to the particle of the type used in this test, these particles act as a catalyst towards CO and NOX. It is believed that the CO is converted to CO2 and water and the NOx are collvelled to N2 and ~2- It is also believed that the rçmetliAtiQn of SO2 was through, at least in part, a catalysis reaction that converted SO2 into other components. The catalyzed re~ction~ were surprisingly achieved even a~
room te""~e, ~tu, ~.

E~ample 3.

The particles made in F.Y~mple 1 were tested for their abilit,v for the removal of various components from water. The test procedures were as follows. For each co,.~ A1~ run, 5 glass columns of 0.875 inch inner ~ meter by 12 inches long were prepared, each having a bed volume of test particle of 95 mls. Each bed wasflushed with five bed volumes of deionized water by dow"w~d pumping at 6 gpm/ft2 of cross-sectional fiow rate (i. e., about 95 mVmin). Each of the flow rates listed in Table 3 is per foot squared of cross-sectional flow rate. Test solutions for each of the aqueous co..~i..-.;"~"l~ were prepared. A total often bed volumes, that is, about one liter per column of aqueous co"~ A"~ test sollltion~ was pumped through each ofthe columns.
- 30 During each lun, the aqueous coll~";l~ test solutions were continuously stirred at low speed prior to entry into the glass column to ".~ ;l, a homogenous composition.

SU~ u~ EEl (RULE2B) i CA 02227428 1997-10-20 WO96/33013 PCTrUS96/05303 During the tenth bed volume, an effluent sample from each column was csllected and analyzed for the particular aqueous c~ ,..,.;"~"l ~Mition~lly, a single influent sample for each test was collected and analyzed for the col,~n,ll;ll,.,ll conce-lLl~ion.

The results of these tests are set forth in Table 3 below.

PARTICLEAQUl~OUS
DESIG- CON- INFLUENT EFFLUENT li LOWDETECTION
NATIONTAMINANT RATE LIMll lt Arsemc 2,890 ppb < 10 ppb 5-6 GPM 10 ppb lu Cadmium 1,003 ppb c10 ppb 5-6 GPM 10 ppb Iv Chlorine 263 ppb <10 ppb 5~ GPM 10 ppb Iw DBCP (sw) 230.0<0.02 ~g/l 5~ GPM0.02 ~g/l 1,2-Dibromo- ~gA '0.02,ug/l 5-6 GPM0.02 ~g/l 3- (sw) 210.0<0.02,ug/1 5-6 GPM 0.02 Chlulu~u~
(gw) 0.07 ~g/l Ix Iron 1.15 m~/l<0.03 mg/l 5~ GPM0.03 ~g/l ly Lead 215 ppb < 10 ppb 5-6 GPM 10 ppb Iz P~ h t. ~ 40.45 mg/l 9.50mg/1 5-6 GPM N/A
laa Radon 1,104.2 303.2 pCi/l 5-6 GPM N/A
pCi/l 306.1 pCi/l 5-6 GPM
911.6 pCi/l I ab Selenium 1.45 mg/l< 0.003 mg/l5-6 GPM0.003 mgtl lac Uranium 50.5 ppm 0.08 ppm 5-6 GPM N/A
sw = Synthetic water gw = ground water E~cample 4.

A particle of 100% activated carbon coconut based of the present invention was prepared in accordance with the procedures of Example 1 above. An S ESCA specl. u.lle~er was used to analyze the surface composition for the original ~SmUTE SHEET (RIJLE 26) WO96133013 PCTrUS96/05303 activated carbon particle and the particle after it was prep2LIed using the process of F.Y~mrle 1. The surface char~ct~i7~tiQn results are as follows.

ACTIVATED CARBON
INllrL~L ACTIVATED PARlICLE OF TEIIS
li T F.l~F.l~T CA]RBON PARTICLE INVENTION
(Atom %)(Atom %) Carbon 96.47 61.65 Oxygen 3.53 16.37 Sodium 0.59 Fluorine 8.61 Potassium 7.60 Chlorine 1.61 Sulfur 0.86 Phosphorus 0-55 ~ "~c;."" 2.5 Thus, the initial particle had an oxygen/carbon ratio of about 0.04, whereas the treated activated carbon particle of this invention had an oxygen/carbon ratio of about 0.27, for an increased oxygen/carbon ratio of about 7 times the original ratio. A similar test was run on 100% ~ mimlm oxide p,ep~ed accolding to the process of Example 1. The oxygen/~ min--m ratio was inclt;ased at least about 2 fold over the original untreated particle oxygen/~ ratio.

Example5.

A TCLP test was run on two di~,e"~ co.~f ~ reme~ tinn applications ofthis invention. The particles were p,~pa,ed by the procedures of Fx~mple 1 and were used to adsorb the particular co.~ in Table 5 below. In accordance with the EPA test rnethods, the particles were, inter alia, washed with an SUBSr~ SHE~T ~RI~LE 26~

W O96/33013 PCTrUS96/05303 acid solution and tumbled for the requisite length of time. The conce..L.~lion of the co~ removed from the particle were then measured. The results are set forth below in Table 5.

TABLE 5 '-EPA TCLP TCLP
PARTICLE CONTAMINANT TEST CONTAMINANT PQL
METEIOD (mg/l) 100%AI203 Lead 1311/6010 C0.50 0.50 100% Al2O3Phosphate 1311/365.4 <o.l2 0.1 PQL is the practical qu~ntit~tion limit, which is an EPA
standard, and is di~e.t.-l than the lowest detect~kle limit.

2 TCLP measures for phosphorus.

Thus, the particles of the invention, when acting as an adsorbent, bond tightly to the COIIInllljl~hlll~

20 Es~mple 6.

A fixed bed reactor was charged with 158 g, 9.4 cubic inches (2 inches di~met~r x 3 inches high) ofthe particles of F.x~mple l(d) (40% Al2O3, 30% V205, 20%
MnO2, 10% TiO2). A mixture of 101.8 ppm NO and 1,035 ppm CO in air was fed into 25 the fixed bed reactor at room tel.~e ~lule at a rate of 35 standard cubic feet per hour (SCFH). The efrluent of the fixed bed reactor was fed into a Horiba CLA-510SS NOX
analyzer and a VIA-510 CO analyzer. The NO concentration dropped imm~di~tely reaching 5.4 ppm by 5 minutes (the first recorded measurement) and continlled to drop to 4.0 ppm by 40 min. (See, Figure 2). The CO conc~ntration d.opped more slowly,30 drol)pi-lg to 532 ppm at 40 min. (See, Figure 3). The test was stopped shortly after 40 minllt~e The CO concenl-~lion was still dec-easi-lg at 40 min. and may decrease further Sl.IBSTl~UI E SHEET (RULE 26) W O96/33013 PCT~US96/05303 -31-upon further reaction time. It is believed that the particles of the invention catalytically degrade the CO and NO.

Throughout this applic~tion~ various public~tiQne are lc;relenced. The 5 tlieclos lres ofthese public~tione in their entireties are hereby h~col~ul~Led by r~rt;lellce into this application in order to more fully describe the state of the art to which this invention pCil l~ns.

It will be app~ to those skilled in the art that various moflific~tiQne 10 and variations can be made in the present invention without dep~Ln~, from the scope or spirit of the invention. Other emlbodi~nents of the invention will be app~t;lll to those skilled in the art from concideration of the spe-~.ifiç~tion and practice of the invention disclosed herein. It is intçn-led that the speçific~tion and ~"~llples be con~ red as ~Y~mpl~ry only, with a true scople and spirit of the invention being in~lic~ted by the 15 following claims.

SUB~ u~ ~httl (RU~ 26)

Claims

What is claimed is:

1. A method for producing an enhanced adsorbent and/or enhanced catalytic particle and/or for producing a catalytic particle, comprising the steps of:
(a) removing an effective amount of air from a closed chamber containing an adsorbent and/or catalytic particle, wherein the resultant chamber pressure is less than one atmosphere;
(b) raising the chamber pressure with an inert gas to at least one atmosphere;
(c) contacting the particle with an energy beam of sufficient energy for a sufficient time to thereby enhance the adsorbent and/or catalytic properties of the particle and/or produce catalytic properties in the particle.

2. The method of Claim 1, wherein the particle comprises an oxide particle or activated carbon.

3. The method of Claim 1, wherein the particle comprises an oxide of metal, an oxide of silicon or activated carbon.

4. The method of Claim 1, wherein the particle comprises aluminum oxide, titanium dioxide, copper oxide, vanadium pentoxide, silicon dioxide, manganese dioxide, iron oxide, zinc oxide, activated carbon, or zeolite.

5. The method of Claim 1, wherein the particle comprises aluminium oxide.

6. The method of Claim 5, further comprising a second particle of titanium dioxide, copper oxide, vanadium pentoxide, silicon dioxide, manganese dioxide, iron oxide, zinc oxide, activated carbon, or zeolite.

7. The method of Claim 1, wherein the particle comprises aluminum oxide and activated carbon.

8. The method of Claim 7, wherein the particle further comprises silicon dioxideand wherein the activated carbon is a mixture of coal based and coconut based activated carbon.

9. The method of Claim 1, wherein the particle is an agglomeration of smaller particles and a binder.

10. The method of Claim 9, wherein the smaller particles are of different composition type.

11. The method of Claim 1, wherein in step (b) the chamber gauge pressure is from 1 psi to 5,000 psi.

12. The method of Claim 1, wherein in step (b) the chamber gauge pressure is at least 100 psi, and further comprising after step (c), rapidly decompressing the chamber pressure to thereby increase the surface area of the particle.

13. The method of Claim 12, wherein in step (b) the chamber gauge pressure is at least 5,000 psi.

14. The method of Claim 1, wherein the inert gas is argon.

15. The method of Claim 1, wherein the energy beam is an ion or electron beam.

16. The method of Claim 1, wherein the method produces a room temperature catalytic particle.

17. A method for producing an enhanced adsorbent and/or enhanced catalytic particle and/or for producing a catalytic particle, comprising implanting oxygeninto an adsorbent and/or catalytic particle.

18. The method of Claim 17, wherein the method produces a room temperature catalytic particle.

19. The method of Claim 17, further comprising increasing the electrical charge on the particle.

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

21. The particle made by the process of Claim 4.

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

23. The particle made by the process of Claim 6.

24. The particle made by the process of Claim 12.

25. The particle made by the process of Claim 17.

26. An enhanced adsorbent and/or enhanced catalytic particle and/or a catalytic particle comprising an adsorbent particle that has been treated to provide an excess of oxygen implanted at least on the surface of the particle to thereby form an enhanced adsorbent and/or enhanced catalytic particle and/or a catalytic particle.

27. The oxygen implanted particle of Claim 26, wherein the oxygen implanted particle has at least 1.5 times the oxygen atom per cent to non-oxygen atom per cent ratio at its surface compared to the initial non-oxygen implanted particle,said surface characterization being determined by an ESCA spectrometer.

28. The oxygen implanted particle of Claim 26, wherein the particle comprises activated carbon and the oxygen implanted carbon has at least 6 times the oxygen to carbon ratio compared to the initial non-oxygen implanted carbon.

29. The oxygen implanted particle of Claim 26, wherein the particle comprises aluminum oxide and the oxygen implanted aluminum oxide has at least two times the oxygen to aluminum ratio compared to the initial non-oxygen implanted aluminum oxide.

30. A binder for binding adsorbent and/or catalytic particles to produce an agglomerated particle comprising colloidal aluminum oxide and an acid.

31. The binder of Claim 30, wherein the acid is nitric acid.

32. A method for binding adsorbent and/or catalytic particles, comprising the steps of:
(a) mixing colloidal aluminum oxide 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.

33. The method of Claim 32, wherein the colloidal aluminum oxide is from 20% to 99% by weight of the mixture.

34. The method of Claim 32, wherein the acid is nitric acid.

35. A method for reducing or eliminating the amount of a contaminant from a liquid or gas stream comprising contacting the particle of Claim 20 with the contaminant in the stream for a sufficient time to reduce or eliminate the amount of contaminant from the stream.

36. The method of Claim 35, wherein the stream is a liquid.

37. The method of Claim 35, wherein the stream is water.

38. The method of Claim 35, wherein the stream is a gas.

39. The method of Claim 35, wherein the stream is air.

40. The method of Claim 35, wherein the contaminant is an organic compound.

41. The method of Claim 35, wherein the contaminant is a heavy metal.

42. The method of Claim 35, wherein the contaminant is carbon monoxide or an oxide of nitrogen or sulfur.

43. The method of Claim 35, wherein the contaminant is acetone, ammonia, benzene, carbon monoxide, chlorine, 1,4-dioxane, ethanol, ethylene, formaldehyde, hydrogen cyanide, hydrogen sulfide, methanol, methyl ethyl, ketone, methylene chloride, nitrogen oxide, propylene, styrene, sulfur dioxide, toluene, vinyl chloride, arsenic, cadmium chlorine, DBCP, iron, lead, phosphate, radon, selenium, or uranium.

44. A method for adsorbing a contaminant from a liquid or gas stream onto an adsorbent particle comprising contacting the particle of Claim 20 with the contaminant in the stream for a sufficient time to adsorb the contaminant.

45. A method for catalyzing the degradation of a hydrocarbon comprising contacting the hydrocarbon with the particle of Claim 20 for a sufficient time to catalyze the degradation of the hydrocarbon.

46. The method of Claim 45, wherein the catalysis reaction is at room temperature.

47. A method for reducing or eliminating the amount of a contaminant from a gas stream by catalysis comprising contacting the particle of Claim 20 with a gas stream containing a contaminant comprising an oxide of nitrogen, an oxide of sulfur, carbon monoxide, or mixtures thereof for a sufficient time to reduce or eliminate the contaminant amount.

48. The method of Claim 47, wherein the catalysis reaction is at room temperature.

49. The method of Claim 47, wherein the contaminant comprises an oxide of nitrogen or carbon monoxide.

50. An apparatus for producing an enhanced adsorbent and/or enhanced catalytic particle and/or for producing a catalytic particle comprising:
(a) chamber means for containing the particle in a closed system having an inlet gas port, an exit gas port, and a target plate, said chamber means being capable of maintaining vacuum and positive pressure;
(b) means for providing an inert gas to the chamber means through the inlet gas port;
(c) means for withdrawing from the chamber means an effective amount of the ambient air therein so as to create a vacuum within the chamber means; and (d) means for providing an energy beam to the chamber means, said energy beam means outlet being targeted at the target plate.

51. The apparatus of Claim 50, wherein the energy beam means produces an ion or electron beam.

52. A method for increasing the surface area of an adsorbent and/or catalytic particle, comprising the steps of (a) raising the chamber gauge pressure of a closed chamber containing the adsorbent and/or catalytic particle to at least 100 psi with an inert gas and (b) rapidly decompressing the chamber pressure to thereby increase the surface area of the particle.

53. The method of Claim 52, wherein the pressure in step (a) is at least 5,000 psi.

54. The method of Claim 52, wherein the surface area is increased by at least 20%.

A method for producing an enhanced adsorbent and/or enhanced catalytic particle and/or for producing a catalytic particle, comprising the step of:
(a) contacting an adsorbent and/or catalytic particle with an energy beam of sufficient energy for a sufficient time to thereby enhance the adsorbent and/or catalytic properties of the particle and/or produce catalytic properties in the particle.

56. The method of Claim 55, wherein the process is continuous.