CA2207039A1

CA2207039A1 - Acid contacted enhanced adsorbent particle and method of making and using therefor

Info

Publication number: CA2207039A1
Application number: CA002207039A
Authority: CA
Inventors: Mark L. Moskovitz; Bryan E. Kepner
Original assignee: Individual
Current assignee: Project Earth Industries Inc
Priority date: 1994-12-07
Filing date: 1995-12-06
Publication date: 1996-06-13
Also published as: IL116276A0; WO1996017682A1; AU4416796A; IL116276A; ZA9510401B; AU708178B2; TW427926B; EP0796145A1; JPH11511687A

Abstract

This invention 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 400 ~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 nonamorphous, non-ceramic, crystalline, 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.

Description

W 096/17682 l~lIU~S/15829 ACID CONTACTED ENHANCED ADSORBENT PARTICLE
AND METHOD OF MAKING AND USING THEREFOR

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION

This invention relates generally to lonh~nre(~ adsorbent particles, particularlyparticles that have been adsorbent enh~n.~ecl by contacting with acid.

BACKGROUND ART

Oxides of metals and certain non-metals are known to be useful for removing COI-.~ ~-I'i from a gas or liquid stream by adsoll,..ll mPrh~nicmc For eY~mrl~, the use of a~;liv~ltd alumina is csn~i~1ered to be an eCon~mir~l method for treating water for the removal of a variety of pollutants, gasses, and some liquids. Its highly porous structure allows for p.~f. ~.llial adsorptive capacity for moisture and co~
co~t~in~cl 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 chlullla~ography and in water purification. Removal of co~ ntc such as phosph~tes by activated ~ min~ are known in the art. See, for example, Yee, W., "Selective Removal of Mixed Phosph~tes by Activated Alumina," J.Amer. WaterworksAssoc., 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 colllposile. The composite is prepared by blending powders of each of the activated carbon and activated alumina conctitllen ~ 30 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 CA 02207039 1997-06-0~
W 096/17682 I~ 5115829 aggloll,cldled. After the water is added, the mix is subjected to a ~h~ping or a formingprocess using extrusion, ~gglomeration, or pelleti7~tion to form a green body. The green body is then heated to a tell~cl~ of 25-100~C or higher. The composite maybe strengthened by p~ h~g by adding nitric acid to the ~ e. It is disclosed that5 the alumina can serve as the binder as well as the absolbcnl. This patent does not use a calcined alumina. Liu et al. discloses an arnorphous alumina trihydrate powder, such as CP2 obtained from Alcoa and an arnorphous alumina trihydrate powder such as CP- I or CP-7, which are recited in U.S. Patent No. 4,579,839, incorporated by ,e~lence in Liu et al. Liu et al. 's use of the term active refers to the surface water being dried and does 10 not refer to a calcined particle. Liu et al. uses acid to strengthen the particle and not to ~nh~nre its adsorbent prop~ . lies. Liu et al. uses an alurnina precursor, which is an absG,l,~ and not an adsorbent.

U.S. Patent No. 3,360,134 to Pullen discloses a composition having adsorption 15 and catalvtic plU~. l lies. Exarnple 2 discloses an alurnina hydrate formed by partially dehydrating alpha-alumina trihydrate in a rotary dryer by counter-current flow with a heated gas and an inlet te,.lpe,~l lre of about 1200~F and an outlet te~llp. l~l~c of about 300~F. The res~lting 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 20 llli~ heated. Exarnple 4 discloses that the procedure of Example 2 was repeated except that calcined alumina was used. The product was unsuitable when calcined nin~ was used. Thus, the acid washed product of Example 2 was not a c~lcinlod alumina.

U.S. Patent No. 4,051,072 to Bedford et al. discloses a ceramic alumina that canbe treated with very dilute acid to neutralize the free ~Ik~linP metal, plinci~ally Na2O, to enable impregnation with catalytic m~t~ri:ll to a controlled depth of from at least 90 to about 250 microns. This patent does not use a cryst~lli7~d al ---i---- .. oxide that has been calcined in accor~ ce with the instant invention. This patent calcines the particle 30 at a t~lllpel~lllC of from about 1700~F to about 1860~F (927~C to 1016~C) to form a ceramic m~teri~l, specifir~lly what is referred to herein as an alpha ~111Tnjn:~

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W 096/17682 1~ 9S/15829 U.S. Patent No. 5,242,879 to Abe et al. discloses that activated carbon materials, which have been subjected to c~l,~ ion and activation l,~A~ and then filrther subjected to an acid l1~A~ t and a heat treAtm~nt~ have a high catalytic activity and are suitable as catalysts for the decornrosition of hydrogen peroxide, ~ S hydl~ines or other water pollutants such as organic acids, 4!lAI~ ~ IIAIY ammonium-salts, and sulfur-co..lA~ .g compounds. Acid is used to remove h~ ies and not to enhAnre the adsoll.~ features. This patent also does not utilize a particle of the instant mvenhon.

Adsoll,tl-l particles of the prior art have not achieved the ability to remove particular contAminAntc from a liquid or gas stream. such as. for example~ a waste stream or drinking water, to acceptably low levels. Additionally, the adsorbent particles ofthe prior art have not been able to bind tightly to particular co~.tA...i~ -tc so that the adsorbent partiClelcontAminAnt composition can be safely disposed of in a 15 IAntlfill. Thus, there has been a need in the art for adsoll,c.ll~ that have improved ability to adsorb particular materials, particularly contAminAntc from a gas or liquid stream, to thereby purify the stream. There has been a need in the art for the adsoll,~llt particles to tightly bind to the adsorbed contAminAnt SUMMARY OF THE INVENTION

In accoldallce 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 PnhAnced adsGll,. ,ll particle comprising contA~ ting a non-amorphous, non-ceramic, 25 crystAllint~ porous, calcined, alllmin-lm oxide particle that was produced by calcining at a particle telll~ of from 400~ C to 700~ C, with an acid for a sufficient time to h~clease the adsorbent l,lo~ ies of the particle.

The invention further provides a process for producing an enh~nred adsorbent 30 particle colllyl;sing contActing a non-amorphous, non-ceramic, crystAllinP, porous, CA 02207039 l997-06-0~

W 096/17682 l~llu~9~ll5829 oxide adso~ particle with an acid for a sufficient time to increase the adsorbent ~,lope.lies of the particle.

In yet another aspect, the invention provides for particles made by the process of 5 the instant invention.

In yet another aspect, the invention provides for a process for red~cin~ or elimin~tin~ the amount of cont~ in a stream cnmrricing cont~cting the particle of the invention with the stream for a sufficient time to reduce or eli...;.lA~e the 10 co..~ tion from the stream.

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

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 ~tt~in~l 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 cl~im.-~

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention may be understood more readily by Icfc.ence to the following detailed description of prefell~d embol1im~ntc of the invention and the Examples included therein.

Before the present compositions of matter and methods are disclosed and ~lescribe~l it is to be understood that this invention is not limited to specific synthetic m~tho-ic or to particular formulations. as such may, of course, vary. It is also to be CA 02207039 1997-06-0~

ood that the terminology used herein is for the pull~ose of describing particular embo.l;..~ only and is not intt~nrled to be limiting.

In tnis specification and in the claims which follow, reference will be made to a 5 number of terms which shall be defined to have the following mP~ninE.c:

The singular forms "a," "an" and "the" include plural ler.,lc.ll~ unless the context clearly dictates otherwise.

"Optional" or "optionally" means that the subsequently described event or circnmet~nre may or may not occur, and that the description includes inet~nreS where said event or circl~rnet~nre occurs and inct~nres where it does not.

The term "particle" as used herein is used h~tcrcllallgeably throughout to mean a 15 particle in the singular sense or a combination of smaller particles that are ~lo~cd 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.
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 producin~ an ~nh~nrecl adso~ particle comprising cont~ctin~ a non-amorphous, non-ceramic, cryst~llinP, porous. calcined, al~ .. oxide particle that was produced by calcining at 25 a particle tc~llp~alule of from 400~ C to 700~ C, with an acid for a sllfficiçnt time to hlcl.,ase the adsorbent ploptliies of the particle. This process can also consist eeeenti~lly of or consist of the particular process steps as described above or further including the additional fealul~es described below.

The invention further provides a process for producing an enh~nced adsorbent particle comprising cont~r,tin~ a non-amorphous~ non-ceramic. cryst~lline, porous, CA 02207039 1997-06-0~

W 096/17682 l~ ,S/15829 oxide adso~ particle with an acid for a sufficient time to increase the adsol~
pro~,.,. Lies of the particle. This process can also consist e~PntiAlly of or consist of the particular process steps as described above or further including the additional features described below.

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 10 eli~--h-A~ g the amount of COI~IAIII;IIAIII!j in a stream comprising contArting the particle of the invention with the stream for a sufficient time to reduce or eliminAte the co--lA...h.AI;on from the stream.

In still yet another aspect, the invention provides a composition comprising the15 particles of the invention.

The particles of this invention have improved or enhAnred adsorptive ~e~ s.
The particles of this invention can adsorb a larger amount of adsorbate per unit volume or weight of adsoll.elll particles than a non-enhAnrecl particle. Also, the particles of this 20 invention can reduce the concentration of col~tA~.~h~A~.Ic or adsorbate material in a stream to a lower absolute value than is possible with a non-~nhAn~ecl particle. In particular embo~;...- .1~, the particles ofthis invention can reduce the cnntAnninAnt cQ~ ..Ir~lion in a stream to below detectAhle levels, never before achievable with prior art pallicles. F.nhAnred adsorptive fe~Lu,es is inten-~.od to include both ion capture and 25 ion çxchAnge ~ rkA~ Ion capture refers to the ability of the particle to bond to other atoms due to the ionic nature of the particle. Ion e~rh~nge is well known in the art and refers to ions being interchanged from one subst~nre to another. 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 30 material.

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W 096/17682 1~ 3S/15829 Not wishing to be bound by theory, it is believed that the acid co..~ g of the particle enh~nres the adsorptive capacily of the particle by adding onto the surface of the particle pores ion moieties present in the acid or present in particle surface water, such as OH, H+, and/or the anion of the acid. The particle covalently or ionically ~ 5 bonds to these ions. It is believed that the particle exhibits an excess and thus an in.;~ased charge in colllp~ison to non-~nh~nrec~ particles.

In the particle of this invention, typically any adsoll,clll particle that is non-oll,hous, non-ceramic, cryst~ n~ porous, has oxygen in the crystal lattice, and can hold a charge, can be used. The particles of this invention are in the crystalline form and are the.efolc non-amorphous. Adso~ particles that are very rigid or hard, are not dissolved to any dcllilllcll~l degree by the acid. and which have initially high, pre-enh~nce<~ adsorptive plu~ ies are l~lcf~llcd. Examples of such particles include, but are not limited to, metal oxides, such as transition metal oxides and Group IIIA and Group IVA metal oxides, and oxides of non-metals such as silicon and ge, jl.AIl;~I~Ç~ ;d adsoll.~ include oxides of a~ .., silicon, m~ng~n~se, copper, vanadium, ~iiconiulll, iron, and LiL~liulll. Even more ~lcr~ d adsolbcnts include al.. inl.. oxide (Al2O3), silicon dioxide (SiO2), m~ngAn~se oxides (MnO, MnO2, Mn2O3, and Mn3O4), copper oxides (CuO and Cu2O), vanadium pentoxide (V2O5), 20 ~ilcomulll oxide (ZrO2), iron oxides (FeO, Fe203, and Fe304), and ~i~liUlll dioxide (TiO2). In an even more ~l~r~..lcd embodiment, the oxide is al~ .. oxide (Al203)that has been produced by c~lrining at a particle telll~ .alulc of from 400~C to 700~C.
These ~l~,r~ ~lc;d ah~ .. oxide particles are preferably in the g~mmA chi-rho, or eta forms. The ceramic form of Al2O3, such as the alpha form, are not included as a part of 25 this invention. In a p~c~ d embodiment, the Al2O3 particles of this invention have a pore size of from 3.5 nm to 35 nm (35A to 350 A) ~i~met~r and a BET surface area of from 120 to 350 m2/g.

In one embodim~nt. the particle is al~min--m oxide that has been pre-treated by 30 a full c~lcin~tion process. Calcined alnminum oxide particles are well known in the art.
They are particles that have been heated to a particular ~elll~e.d~e to form a particular CA 02207039 1997-06-0~

W O96/17682 1~ 9S/15829 crystalline structure. P,ocesses for making calcined al~ .. 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., Ac~demic Press (1970), which is incoll.olaled by reference herein. In one embo~timt nt the Bayer process can be used to make al .-;.. oxide5 p~ ,ula~ . Also, pre-calcined alllminllm oxide, that is, the al~...;...l... oxide p~ O~
(Al(OH)3), and calcined al~.. ;.. oxide are readily collllllc.~;ially available. ~lcin~cl al~ " 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 of the particle. However, it is preferable to ,.,;.~;,..i7.o the deactivation to IIIAX;.II;~- the 10 adsGll,~ capability. In some lef.,.ellces in the prior art, "activated" refers only to the surface water being removed from the particle to h1clcase its adsorbent ability.However, as used in reference to the instant invention, activated refers to a particle that has first been c~lcinrc~ and is then also m~int~in~i in its dried state. Thus, as used herein, all active particles of the invention have also been calcined. The particles are 15 not limited to any physical form and can be in the particulate, powder, granular, pellet, or the like form. The particles are preferably in a gel state.

The acid that can be used in this invention can be any acid or llli~Lule of acids that can add extra ion moieties onto the surface of the pores of the oxide particle.
20 Typical ion moieties include OH, H+, and the anion of the acid. Examples of such acids include, but are not limited to, nitric acid, sulfuric acid, hydlochloric acid, boric acid, acetic acid, formic acid, phosphoric acid, and mixtures thereof. In a plef~,lled em~lo~tim~nt, the acid is acetic acid bec~e 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 ...~x;...l..,. or saturated loading of the ion moieties on the particle. For example, a 0.5 wt. % and even a 0.1 % acetic acid solution has been found effective.
30 However, a wide range of co~rentrations of acid can be used in this invention from very dilute to very concelll.a~ed depending on the hazards involved and the economics CA 02207039 1997-06-0~

WO g6/17682 PCI/US95/15829 of production. However, if the acid is too concellLl~ted, it will etch the particle c~llcing an h~cl~ase in lllacrol~ulc;s while eli...;..~ e micropo-es, which is detrimental to the particles of this invention. Thus, the acid tre~tment is preferably of a concentration and length of time to be more than a mere surface wash but less than an etc.hinp.
5 Additionally, the acid preferably has some water present to provide OH and/or Ht ion moieties, which bond with the particle. When the acid is diluted with water, the water is preferably distilled water to ~ lli7~ the amount of inl,u~;Lies contacting the particle.

The particle of the invention is made by the following process. The particle is cont~Gted 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 variesaccording to the ability of the particular particle to be saturated with the ion moieties.
15 The time can be as low as a few ...il..~ s, at least 15 ...il~ es at least one hour, at least 6 hours, at least 12 hours, or at least one day, to assure saturation. The time must be sufficient to at least incl. ase the adsorbent pl~p~ llies of the particle by adding ion moieties to the particle. In one embo~lim~nt7 the particle is submerged in the acid, and saturation is typically complete when the particle stops bubbling. The contacting 20 should be sl1bst~nti~l enough to provide penetration of the acid throughout the pores of the particle. Mere washing the outside surface of the particle to remove i~ ies is not sllfficient to provide adequate penetration of the acid into and throughout the pores of the particle.

The acid co,ll~cled particle is then optionally rinsed. Rinsing insures that theparticle does not later release acid concentrated dust that may become airborne and which can be inh~led Rinsing of the acid contacted particle does not reduce the enh~nced adsorptive capability of the particle. When rinsed. the particle is preferably rinsed with distilled water to ...;l~ h~ y contact.

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W 096/17682 ~ 7S1l5829 Optionally, the particle is dried by a low to moderate heat Ll~ to remove excess liquid, such as acid or water, from the rinsing step to thereby hlc~ease the activity of adsorption. Drying of the particle also reduces the transfer cost of particle.
However, the particle is not calcined or recalcined after acid ll~A~ f .l Such 5 recalcining would detrimPntAIIy change the surface characteristics by closing up the mlcro~ ,5.

The size of the particles used in this invention can vary greatly ~epen~ing on the end use. Typically, for adsorption or catalytic applications, a small particle size such as 10 20 ~m or greater are preferable because they provide a larger surface area than large particles.

The particle of this invention can be used in any adsorption or ion capture application known to those of oldin~y skill in the art. In one embodiment, the particle 15 is used for envirol....- ..IAI rPmPAiAtio~ applir~ti--~c In this embo-limPnt the particle can be used to remove co~.~h~..h-At-ts, such as heavy metals, organics, including hydrocarbons, inG~ ics, or lllix~ s thereof. Specific examples of col~A.Il;"~t..~;
include, but are not limited to, acetone, microbials such as cryptosporidium, ammonia, bPn7PnP chlorine, dioxane, ethanol, ethylene. forrnAIcle-hyde, hydrocarbon cyanide, 20 hydrogen sulfide. methanol, methyl ethyl ketone. methylene chloride, propylene, styrene. sulfur dioxide, toluene, vinyl chloride, arsenic, lead. iron, phoslJhAles, selel~ lll, cadmium, Ul~iUlll, radon, 1,2-dibromo-3-chloluplup~le (DBCP), chromium, tobacco smoke, cooking fumes, zinc, and trichloroethylene. The particle of this invention can reme~liAte individual co..l;i...;..A~ or multiple co.llA...i..A~ from a 25 single source. In e~Pn~e~ anywhere ions are used to capture pollutants, this invention achieves improved efficiency by adsorbing a higher arnount of COIIIAIIl;l1AIII~ and by rPd~cin~ the co,.lA~ AIion level to a much lower value than by non-enhAnçe~ particles.

For enVironm~ntAl remP~IiAtion applications, particles of the invention are 30 typically placed in a container, such as a filtration unit. The cnntAmin~tç~l stream enters the co~.lAi~-f ~ at one end, contacts the particles within the cQrltAinPr~ and the purified CA 02207039 1997-06-0~

WO 96/17682 PCr/US95/15829 stream exits through another end of the container. The particles contact the co~ AIll~i within the stream and bond to and remove the co~ tion from the strearn. Typically, the particles become s~luldled with col-tA~-~it-A~t~ over a period of time, and the particles must be removed from the co. l~ r and replaced with fresh 5 particles. The co.-t~...;..~..~ strearn can be a gas strearn or liquid stream, such as an aqueous stream. The particles can be used to reme~i~tP~ for example, waste water, production facilit,v ~rnu~ tr smoke stack gas, auto exhaust, drinking water, and the like.

The particle of the invention can be used alone, in combination with other 10 particles plepa.ed by the process of the invention, and/or in combination with other adsorbent particles known in the art. The particles can be combined in a physical ule or agglo"" .aled using techniques known in the art, such as with a binder. to form a mullirw,clional composite particle.

In one embo~imPnt the invention is directed to a composition comprising an al~ .. it.. oxide particle made by the acid ~nh~nrin~ process ofthe invention. In a fu~her embo~im~ont~ this composition further cornpri-cps a co-adsorbent particle. This co-particle is preferably any adsorbent particle known in the art. Such co-adsorbent particles can be preferably non-amorphous, non-ceramic, cryst:lllinP, porous, oxide 20 adsorbent particles, more preferably silicon dioxide, or a metal oxide. such as -Pse oxides (MnO, MnO2, Mn203, and Mn304), copper oxides (CuO and Cu20), V~n~ lm pentoxi~e ~2~5)~ zirconium oxide (ZrO2), iron oxides (FeO, Fe2O3, and Fe3O4), and li~ ;.,... dioxide (TiO2). The co-particle can acid-enh~nred or non-acid enh~nred In a ~,~r~ d embo~ime~t, the co-particles are not acid-enh~nced In a ~,er.,l,~,d embodiment. the composition comprises alllminum oxide made by the acid enh~nred process of the invention, copper oxide, and m~ng~n~se oxide.
Preferably, these components are in a plopo,lion of from 50-98 parts, more preferably 80-95 parts~ even more preferably 88 parts acid enh~nre~ al~.. ;.. oxide; and 1-49 30 parts, more preferably 4-19 parts, even more preferably 6 parts of each of copper oxide and m~n~nrse oxide. Preferably, the composition is held together using a colloidal CA 02207039 1997-06-0~

W O96/17682 P~ln~9S/15829 - 12-~Inmin~ binder that has been crosclink~ as described below. In a l,l.,r.,.l~,d embo-iimPnt, this collll)osilion can be used to reme~ te organics, such as hyLoc~l,olls, even more plefeldbly, 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-çnh~n~ecl alllminllm oxide/co-particle embodiment of the invention to rem~ te organic corlt~min~ntC is due to a catalytic degradation of the organic co.~t~..;n~ even at room tcll~ Lule. This catalytic activity is possiblypresent becausc the inventive co-particle was ch~llenped with a high concelllldlion of 10 organic col.~ c and no organic cont~min~ntC were found on the surface of the particle by visual observation or on the residual solution after TCLP analysis. In a prcÇ~ d embo~im~ns, the Al2O3 in combination with one or more oxides of m~ng~nPse, copper, and/or iron are particularly suited to possibly catalytically degrade organics, such as hydrocarbons and trichloroethylene.
Binders for binding the individual particles, either of the same or dirr.,~el~
types, to form an agglomerated particle are known in the art or are described herein.
Binders that do not intelr~c with the adsoll~elll features are pler. ll~d. In a p,er.,l,~,d embo~im~nt! the binder can also act as an adsorbent. A ple~cll~d binder for the 20 agglomerated particle is colloidal alumina or colloidal silica. At approximately 450~C, the colloidal alumina goes through a ~ ro~mation stage and cross-links with itself.
Colloidal silica cross-links with itself if it is sufficiently dried to remove water.
Preferably, from about 5 wt% to about 99% of the total adsorbent particle lllixlulc is colloidal alumina or colloidal silica to provide the n~cec~ y crocclinking during 25 heating to bind the agglomerated particle into a water-resistant particle. The particle can then withstand ex~osulc to all types of water for an extended time and not degrade.

In one embo~lim~nt, the agglomerated particle is made by mixing colloidal alumina with the adsorbent particles of the invention. Preferably, the acid çnh~nred 30 particles have been produced and are ready for agglomeration prior to mixing with the acid below. Typically, from about 5% to about 99%, more preferably 20%, by weight of the IlliXlU~'l~iS colloidal alumina. The particle mixture is then mixed with an acid solution such as, for example, nitric, sulfuric, hydrochloric, boric, acetic, formic, phosphoric, and ~ S thereo~ In one embodiment the acid is 5% nitric acid solution. The colloidal alumina, adsorbent particles, and acid solution are thoroughly 5 rnixed so as to create a homogenous blend of all elemPnt~ Then additional acidsolution is added and further mixing is p. ,ro,l.lcd until the mixture reaches a suitable concictpnry for agglomeration. Preferably, the mixture is then extruded and chopped up into the desired size. The resllltAnt particles are heated to at least 450~C to cause the colloidal alumina crosclinking to occur.
The particle of this invention bonds with the cont~rnin~nt so that the particle and CO~IIA~ A-II are tightly bound. This bonding makes it difficult to remove the COI~IA~II;IIA~I from the particle, allowing the waste product to either be ~licposed of into any public landfill or used as a raw material in the building block mAnllf~ctllring 15 industry. M~ul. ~ of COI~tA~ A~I~ C adsorbed on the particles of this invention using an EPA Toxicity Ch~ac~.istic T e~ch~bility Procedure (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 cor.l~ i..AI~tc 20 F~eriml~ntAl The following examples are put forth so as to provide those of onii-.~ y skill in the art with a complete disclosure and description of how the compounds clAimP~lherein are made and evaluated, and are int~n~ed to be purely exemplary of the 25 invention and are not int~nd~d 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, t~ p~,dlLIre, etc.) but some errors and deviations should be accounted for.
Unless indicated otherwise, parts are parts by weight. tel~ ldLUleiS in oC and ples~ule is at or near atmospheric.

CA 02207039 1997-06-0~

WO 96/17682 PCI~/US95/15829 E~mPL~ 1-Fnh~nt ed al1lminum oxide particles were made by the process of this invention.
mm~ al!~..in~.. oxide particles were produced by calcining Al(OH)3 at a particle5 telllpc.~tul~ of 550-560~C. 20 liters of this al - ..i.. ~ . oxide were subnl.,.~ed in a tank co~ il.g 0.5% by weight acetic acid in ~ tilled water. The total volume of solution was 15.56 liters. The alumina was allowed to sit for approximately 15 mimltes to allow saturation ofthe solution. The acid solution was drained offand the le "Ai";"g alumina was rinsed in a tank of 30 liters of distilled water. The riictilled water was drained and 10 the r~m~ining alumina was dried at a tell~ ulc of 121 ~C for 90 minlltçs The l,..r~l.l.ance of enhanced all-minllm oxide particles of this invention was tested. Two chromatographic columns, each 25 cm. long and I cm. inner ~ metçr~
equi~ped with a solvent reservoir were used for this experiment. Each column was15 packed with 20 cc of the above produced enh~nred al~min-~m oxide particles. Each column was flushed with 100 ml of water using ~Jre~Ul~ from the a nitrogen cylinder to obtain a flow rate of approximately 20 ml per minute. A test solution of approxim~tçly 200 ppb of lead was pl~ed using lead acetate trihydrate. A total of 200 ml (10 bed volumes) of test solution was passed through each column using the same flow rate.
20 The influent. the total effluent from the 10 bed volumes. and the effluent sample collected during the tenth bed volume were analyzed for lead. The results are set forth in Table 1 below.

0 .1 0 0 00 0 0 0 3 o o o ~ O
'i -~5--T~BLE I
TESTN~P~R STREAM ~ TOTh~LEA~
c~ugm/liter) I rnfluc~nt 211 .
Tntal e~luent : ~ 5 ~7.ffl~l~nt end (lOth bed ~rolume)~5 2 Tnfl-le~ 229 Total effluent - ~5 Fffhlent end (lOth bcd volume) . ~5 Lower limit of lead dcl~cl;on w. s S ~gm/liter.
~- tO
~, ~

E~ArqPIe ~ -A compalison was made ~ ,cn ~ n~ ofthis ill~ltiG~ and non-treated 15 alumina for rcmovingleat. Fnh~ ~ gamma~ "o~adep~rticlesofthepresent ,tion wae madc accol~i.g to the pr~ccJu~ of F- ~~'~ 1. Two id ~l:c~l five gallon (22 lita) c4n~inPrS were filled wi~ the ~ ng o~de for lead ~mo~l. One CoA~ ~. r was filled with 16 liters ofthe treated ~ m;~ ofthis invention. The other was Sllcd with 16 liter~ of u-~uc~t~d P~ nina Two t~s were pr~ each col~
20 gallon~ (440 liters) of lead acctate tn-hydrate spiked ~;~ll~d w~;ter. The tanks were t s ~ d thoroughly for 30 rn;n~t~ Mcr 30 n~inuta of mixin& the eQn~ tl atiOnS of thc . .-~
lead ut the wata were determinot. Tho lo~d c~ C watcr ~om each tsnk was ps~ed through ~te co~t~ of ~ m;~9 A tot~l of 80 g~llon~ (352 litcr5) of spiked water (16 bed voluma) were passed throulch each of the co~l A; . ~ ~ ~ at a flow rate of 62 25 gallons (273 liters) per minute. An eflll~cnt wat~r sample was t~en on the 16th bed volume and was anal~ for total lead. The percent rcd~t~ n~ were then c~ ote~l The results of thc tests are set forth in Table 2 below.

P~RTICLEINll~AL LE~D E~UENT PERCEI~T
CONCENI~lION CONCENTRATION REDUCI'ION
(mg/l) ~mR CONTACI'ING OF LE~D
P~ll~ (%) (m~) Non-treated 1.24 0.58 47 ~11....;..,.... oxide Treated ~1.. ;......... 1.44 0.39 74 oxide of the invention E~amnle 3.

A col,lp~isoll was made bet~een treated ~ min~ ofthis invention and non-15 treated ~lllmin~ for removing phosph~te Chi-rho ~lllmimlm oxide particles were produced by c~l-ining Al(0H)3 at a particle t._",pe.~l-lre of 480-520~C. Fnh~nced chi-rho ~lllmimlm oxide particles ofthe present invention were then made acco,ding to the procedures of FY,; ..~ C 1. The p~,~""ance ofthe particles was measured using the same procedures of Example 1, except that one chl o",dlographic column was filled with 20 20 cc ofthe treated ~lllmin~ and the other column was filled with 20 cc ofthe untreated ~lllmin~ and the test solution was 9.3 mg/l of KH2PO4. The results ofthe tests are set forth in Table 3 below.

SUBSTITUTE SHEET (RULE 26) 'J O O l-)t~ ~ O
' ' ~ O ';3 ~, 0 0 ~ O
O ~~ o o O ~ O ' ~

-~7~

T~L~: 3 ~ ~ . -P~RTICLE~ INITI.~L EFFLlnZNT PEI~CE~
PHOSPl~TE CONCENSR~TION ~DVCTION: -CONCENT~TIOI'~ AFI ER CONT~CT~G OF~
(mg/l) (mg/l) (y Non-treated - 9.3 0.16 98.3 S alununum o~ate Treated ~ m 9 3 0 04 99.6 : -:
oxide of the invention . ' E:~am~le 4 ~he ability ofthe particle ofthis i~ tion to remove selenium was tested. Acid 15 enhallçe~ ganUIla ~ min~ oxide particles (100% A12O3) were made by the procedure of Fy~mple 1.

S collurn~ werc prep~ ing 0.875~ I.D. x 12" (2.2 cm I.D. x 30.5 cm)jong glass ~ mr~, each witb ~ bed volumo of -95 mls of thc ~o~rc ACit cnhanccd ~ ~ O320 par~cles ofthis invention of various pa ticle ~izes, ranging ~om 500 llm to 4,000~,um.- ~
!- '- Each bed was flu~hed with -~ bed volumes of I.D. wa~er by do~. n. .ud pumping ât 5-6 ~ ~ -gpm/~2 cross s~ ;Q~ flow rate (i.e., -95 ml/min). A test s~hltior was prepared with a :
calculatet 1.5 mg/L ~t~ A total of -10 t~ed volumes (~.e., -1 1, per cQll)~n) test so'ution was pumped through each column using the same flow ra~e. During the test, -~ ~
25 the test s~ution was continnQucly ~tirred at a low spect. Dunng the tenth bed volume, ~ :
an e~uen~ sample from each column was c~'lxte~ ~t analyzed for ~enium Also a-single Influent sample was colleete~ ant anaJ~cd for Selen;um The results are set forth :
bdow.

. . ~ . , .

WO 96/17682 PcrluS9S/15829 Sample I.D. Total Seleniuma (particle size ~m) m~/L
TnflllP!nt 1.45 S 606 EFF (4,000 ~m) 0.101 404 EFF (1,000 llm) 0.073 303 EFF (2,000 ~m) 0.477 202 EFF (S00 ~lm) 0.0o3b 101 EFF (3,300 llm) 0.121 ~0 a = Selenium detection limit was 0.002 mg/l b = Fctim~t~-d value, less than calibration limit F~ ?le 5 A combination particle of this invention was made and tested for its ability to remove trichloroet-h-ylene. 70 g of acid enh~nred gamma ~ .";~ ." oxide particles 20 made by the procedure of Example I were mixed with 20 g of alumina type gel, 5 g of Mn2O3, and 5 g of CuO until the mixture was homogeneous. The particle lllixlure was then mixed with 5% nitric acid solution until the mixture reached a suitable con~ict~ncy for agglomeration. The mixture was extruded and cut into a particle size of about 1,000 ~m and heated to 500~C for IS ll~ lUIeC to crosslink the colloidal alumina.
Two cl~olllatographic columns (24 cm x 8 mm) each co..~ h-~ 3 ml (dry) volu nes of the above produced Al203/CuO/Mn203 combination particle of the invention were charged with S x I bed volume of (a) I ppm trichloroethylene (TCE) in deionized water and (b) 1 ppm VOA matrix spike mix (also co~ I ppm TCE) in 30 deionized water, l~ ,c~lively. The I ppm VOA stock solution was obtained by dilution (deionized water) of a 1000 ~g/ml VOA mix (Supelco) which cont~ined the following analytes in mt~th~n-l; (I) benzene, (2) chlorob~n7Pne7 (3) toluene, (4) trichloroethylene, and (~) l,l-dichloroethylene. The other stock solution (I ppm TCE in water) was W O 96/17682 1~1/U~Stl5829 obtained by dissolving 0.01 g spe~,ln)photometric grade TCE (Aldrich) in deionized water followed by dilution to a liter. The fifth bed volume from each column wascollected (no h~rlcp~r,e) in 2 ml screw-cap vials with Teflon-coated silicone septa and stored on ice prior to GC/MS analysis (EPA Method 8260). The results are as follows.

Trichloroethylene concentration Sorbate Influent (ppm) Effluent (ppb) TCE in water 1.0 <50 VOA mix in water 1.0 <50 F,-~le 6 TCE adsorption and TCLP extraction procedures were p.,.rulllled as follows. A
20.0114-gram (about 24.50 bed volume) sample of the Al2O3/CuO/Mn2O3 combination 20 particle of Example 5 (deci~n~ted as 0307595TCEl) was wet packed into a 50-mLburet (with removable stopcock) plugged with glass wool. The sample was charged with five bed volumes of water. The sorbent material was then ~ ely sr..l~;d into the Zero H~epa~e Extractor (ZHE) ap~lus into which 200 mL of water was added, ap~l~l;ately sealed and agit~t~d for 18 hours. The filtered solution 25 was collected in two 100 mL vials, stored in the refrigerator at 4~C until analysis by GC/MS. The Finnig~n MAT ~gmlm ion trap GC/MS equipped with a Tekrnar liquid sample conct;llll~lor (LSC 2000) was used for analysis.

The calibration curve procedure was as follows. A freshly ~ ed 50 ppm 30 TCE stock solution was obtained by dissolving 34.2 ~11 spectrophoto,l~ ic grade TCE
(Aldrich) in 20 ml HPLC grade m~th~nol (Fisher) followed by dilution to a liter.Dilution ofthis solution (lû00 ~1: lL) resulted in a 50 ppb TCE stock solution. All CA 02207039 1997-06-0~

WO g6/17682 P~ ,95115829 dilutions were ~cco~ h~d using deionized water. A calibration curve was constructed by ~U~ lg 1.0, 0.50, 0.20, 0.10, and 0.050 ppb TCE solutions.

The results are set forth below.

Sorbent Sample TCE found, ppb TCE Detecti~n limit, ppb 0307595TCEI Nda 0.0050 a = Not detectP~l The fact that TCE in the sarnple is less that 500 ppb (EPA TCLP limit) char~cteri7~s it as a nonhazardous waste with respect to TCE.

Throughout this application, various publications are lcr~lenced. The disclosures of these publications in their entireties are hereby inco.~ol~ted by Icç,l~llce into this application 15 in order to more fully describe the state of the art to which this invention pCl ~ S.

It will be al p~.,llt to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other embo~i..,t~ ofthe invention will be ap~ cnt to those skilled in the art 20 from consideration of the specification and practice of the invention disclosed herein. It is int~ntled that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being intli~ted by the following claims.

Claims

What is claimed is:

1. 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 400°C
to 700°C, with an acid having a dilute concentration for a sufficient time to increase the adsorbent properties of the particle, wherein, the acid concentration and the contacting time provides an acid contacting with the particle that is greater than a surface wash but less than an etching of the particle, and wherein the resultant acid treated aluminum oxide is not subsequently calcined or recalcined.

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

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

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

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

6. The process of Claim 5, further comprising the step of drying the particle.

7. The process of Claim 1, wherein the contacting is for at least 15 minutes.

8. A process for producing an enhanced adsorbent particle comprising contacting a non-amorphous, non-ceramic, crystalline, porous, oxide adsorbent particle with an acid having a dilute concentration for a sufficient time to increase the adsorbent properties of the particle, wherein, the acid concentration and the contacting time provides an acid contacting with the particle that is greater than a surface wash but less than an etching of the particle, and wherein the resultant acid treated oxide adsorbent particle is not subsequently calcined or recalcined, wherein the oxide adsorbent particle is not aluminum oxide.

9. The process of Claim 8, wherein the oxide adsorbent particle is silicon dioxide, manganese oxide, copper oxide, vanadium pentoxide, zirconium oxide, iron oxide, or titanium dioxide.

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

11. The particle made by the process of Claim 3.

12. The particle made by the process of Claim 8.

13, The particle made by the process of Claim 9.

14. The particle of Claim 10, wherein said particle passes the EPA TCLP test for lead.

15. A process for reducing or eliminating the amount of contaminants in a liquid or gas stream comprising contacting the particle of Claim 10 with the liquid or gasstream for a sufficient time to reduce the amount of or eliminate the contamination from the liquid or gas stream.

16. The process of Claim 15, wherein the stream is liquid.

17. The process of Claim 15, wherein the stream is gas.

18. The process of Claim 15, wherein the contaminant is lead, phosphate, selenium, or zinc.

19. A composition comprising the aluminum oxide particle made by the process of Claim 1.

20. The composition of Claim 19, further comprising a second oxide adsorbent particle.

21. The composition of Claim 20, further comprising an aluminum oxide gel binder.

22. The composition of Claim 19, further comprising silicon dioxide, manganese oxide, copper oxide, vanadium pentoxide, zirconium oxided, iron oxide or titanium dioxide.

23. The composition of Claim 19, further comprising copper oxide and manganese oxide.

24. The composition of Claim 23, wherein the composition comprises 50-98 parts of said enhanced aluminum oxide, 1-49 parts of said copper oxide, and 1-49 parts of said manganese oxide.

25. The composition of Claim 23, wherein said composition passes the EPA TCLP test for trichloroethylene.

26. The composition of Claim 23, wherein said copper oxide is CuO and said manganese oxide is Mn2O3.

27. A process for reducing or eliminating the amount of an organic contaminant in a liquid or gas stream comprising contacting the composition of Claim 23 with the liquid or gas stream for a sufficient time to reduce the amount of or eliminate the organic contaminant from the liquid or gas stream.

28. The process of Claim 27. wherein the organic contaminant is trichloroethylene.

29. The process of Claim 27, wherein said reduction or elimination is by a catalytic degradation process.

30. The process of Claim 1, wherein the dilute acid concentration is equivalent to an aqueous acetic acid solution at least than or equal to 0.5% by weight.

31. The process of Claim 1, wherein the dilute acid concentration is equivalent to an aqueous acetic acid solution at less than or equal to 0.1% by weight.

32. The process of claim 1, wherein the calcined aluminum oxide is in the gamma, chi-rho, or eta form.

33. The process of Claim 1, wherein the aluminum oxide particle is not sintered.

34. The process of Claim 1, wherein the particle consists essentially of aluminum oxide.

35. The process of Claim 1. wherein the particle consists of aluminum oxide.

36. The process of claim 1, wherein the aluminum oxide particle is not an adsorbent support or a catalyst support.

37. The composition of Claim 20, further comprising a colloidal aluminum oxide binder or colloidal silicon dioxide binder.
'

38. The composition of Claim 20, further comprising a colloidal aluminum oxide binder.

39. The composition of Claim 23, further comprising a colloidal aluminum oxide binder or colloidal silicon dioxide binder.

40. The composition of Claim 23, further comprising a colloidal aluminum oxide binder.

41. The composition of Claim 23, wherein said copper oxide is CuO and said manganese oxide is MnO2.

42. A composition comprising the acid treated oxide particle made by the process of Claim 8 and further comprising a colloidal aluminum oxide binder or colloidal silicon dioxide binder.

43. A process for producing an enhanced adsorbent particle comprising contacting a non-ceramic, porous, oxide adsorbent particle with an acid having a dilute concentration for a sufficient time to increase the adsorbent properties of the particle, wherein, the acid concentration and the contacting time provides an acid contacting with the particle that is greater than a surface wash but less than an etching of the particle, and wherein the resultant acid treated oxide adsorbent particle is not subsequently calcined or recalcined, wherein the oxide adsorbentparticle is not aluminum oxide.

44. The process of Claim 43, wherein the oxide adsorbent particle is silicon dioxide, manganese oxide, copper oxide, vanadium pentoxide, zirconium oxide, iron oxide, or titanium dioxide.

45. A composition comprising the acid treated oxide particle made by the process of Claim 43 and further comprising a colloidal aluminum oxide binder or colloidal silicon dioxide binder.

46. A composition comprising an aluminum oxide particle made by the process comprising contacting a non-amorphous, non-ceramic, crystalline, porous, calcined, aluminum oxide particle that was produced by calcining at a particle temperature of from 400°C to 700°C, with an acid for a sufficient time to increase the adsorbent properties of the particle.

47. The composition of Claim 46, further comprising a second oxide adsorbent particle.

48. The composition of Claim 47, further comprising an aluminum oxide gel binder.

49. The composition of Claim 46. further comprising silicon dioxide, manganese oxide, copper oxide, vanadium pentoxide, zirconium oxide, iron oxide or titanium dioxide.

50. The composition of Claim 46, further comprising copper oxide and manganese oxide.

51. The composition of Claim 50, wherein the composition comprises 50-98 parts of said enhanced aluminum oxide, 1-49 parts of said copper oxide, and 1-49 parts of said manganese oxide.

52. The composition of Claim 50, wherein said composition passes the EPA TCLP
test for trichloroethylene.

53. The composition of Claim 50, wherein said copper oxide is CuO and said manganese oxide is Mn2O3.

54. The composition of claim 50, wherein the aluminum oxide particle is not an adsorbent support or a catalyst support.

55. The composition of Claim 50, wherein said copper oxide is CuO and said manganese oxide is MnO2.

56. The composition of Claim 53, further comprising a colloidal aluminum oxide binder or colloidal silicon dioxide binder.