Adsorption, ChE468/ChE568, Fall2005

Chapter 4. Adsorbent Materials

4.1 Introduction The adsorptive separation is achieved by one o the three !echanis!s" steric, #inetic or e$%ilibri%! e ect& The steric e ect derives ro! the !olec%lar sievin' properties o (eolites and !olec%lar sieves, as ill%strated in Fi'%re 4&)& *n this case only s!all and properly shaped !olec%les can di %se into the adsorbent, +hereas other !olec%les are totally e,cl%ded& -inetic separation is achieved by virt%e o di erences in di %sion rates o di erence !olec%les& An e,a!ple o #inetic separation is .2//2 in carbon !olec%lar sieve& Fi'%re 4&2 sho+s the di erent di %sion rate o .2 and /2 in carbon !olec%lar sieves, +hile Fi'%re 4&0 indicates that carbon !olec%lar sieve has no e$%ilibri%! separation or .2 and /2& A lar'e !a1ority o processes operate thro%'h the e$%ilibri%! adsorption o !i,t%re and hence are called e$%ilibri%! separation& A typical e,a!ple o e$%ilibri%! separation is /2/.2 on (eolite 5A as sho+n in Fi'%re 4&4& 2ost solid are able to adsorb species ro! 'ases and li$%ids& 3o+ever, only a e+ have s% icient selectivity and capacity to !a#e the! serio%s candidates or co!!ercial adsorbents& .nly o%r types o 'eneric adsorbents have do!inated the co!!ercial %se o adsorption" activated carbon, (eolite, silica 'el, and activated al%!ina& Esti!ated +orld+ide sale o these adsorbents are" Activated carbon" 6eolite" 8ilica 'el" Activated al%!ina" 4) billion5 4)007)000 !illion5 429790 !illion5 426790 !illion&

:oly!eric ion7e,chan'e resin has a si'ni icant !ar#et in +ater treat!ent and pac#in' !aterials or ;C and 3:<C col%!ns& E,a!ples o co!!ercial adsorbents applications are 'iven in Table 4&)& The representative physical properties o the adsorbents disc%ssed above are s%!!ari(ed in Table 4&2& The adsorbent characteri(ation !ethods +ill be disc%ssed in detail in the ne,t section&

Adsorption, ChE468/ChE568, Fall2005

Fi'%re 4&) 8#etch sho+in' the !olec%lar sievin' e ect or nor!al and iso7para ins in a 5A (eolite

Fi'%re 4&2& 8#etch o the ractional %pta#e rates o o,y'en and nitro'en in !olec%lar sieve carbon

Adsorption, ChE468/ChE568, Fall2005

Fi'%re 4&0 8#etch o e$%ilibri%! o o,y'en and nitro'en on !olec%lar sieve carbon at 20 C&

Fi'%re 4&4 8#etch o e$%ilibri%! isother!s o o,y'en, nitro'en and ar'on on (eolite 5A at 20 C

Adsorption, ChE468/ChE568, Fall2005

Table 4&) E,a!ples o Co!!ercial Adsorbents Applications

Adsorption, ChE468/ChE568, Fall2005

Adsorption, ChE468/ChE568, Fall2005

Table 4&2 =epresentative :roperties o Co!!ercial Adsorbents

Adsorption, ChE468/ChE568, Fall2005

To be s%itable or co!!ercial applications, an adsorbent sho%ld have >)? hi'h selectivity to enable sharp separations, >2? hi'h capacity to !ini!i(e the a!o%nt o adsorbent needed, >0? avorable #inetic and transport properties or rapid sorption, >4? che!ical and ther!al stability, incl%din' e,tre!ely lo+ sol%bility in the contactin' l%id, to preserve the a!o%nt o adsorbent and its properties, >5? hardness and !echanical stren'th to prevent cr%shin' and erosion, >6? a ree7 lo+in' tendency or ease o illin' or e!ptyin' vessels, >9? hi'h resistance to o%lin' or lon' li e, >8? no tendency to pro!ote %ndesirable che!ical reactions, >@? the capability o bein' re'enerated +hen %sed +ith co!!ercial eedstoc#s that contain trace $%antities o hi'h7 !olec%lar7+ei'ht species that are stron'ly adsorbed di ic%lt to desorb, and >)0? relatively lo+ cost&

4.2

Adsorbent Characterization The !ost i!portant characteristic o an adsorbent is its hi'h porosity& Th%s physical

characteri(ation is 'enerally !ore i!portant than che!ical characteri(ation& The !icroporo%s str%ct%re o adsorbent can be characteri(ed by standardi(ed techni$%es& The !ost i!portant physical characteristics incl%de pore vol%!e, pore si(e distrib%tion, and speci ic s%r ace area& Also o practical i!portance are b%l# density, cr%sh stren'th, and attrition resistance& Adsorption 9

Adsorption, ChE468/ChE568, Fall2005

properties o an adsorbent incl%de e$%ilibri%! capacity or #inetic capacity, di %sivity and separation actor&

4&2&)

8peci ic s%r ace area >AET s%r ace area, !2/'? A !icroporo%s adsorbent can have very lar'e speci ic s%r ace area >B)000 !2/'? beca%se

it has very ine pores& * +e ass%!e the pores in adsorbent to be cylindrical +ith a dia!eter o dp and len'th o <, the ollo+in' e$%ation clearly de!onstrates the relationship bet+een pore si(e and speci ic s%r ace area, and s%r ace are7to7vol%!e ratio" 8 >!2/'? C >Dd:<? : / E>Dd:2</4?FG:H C 4 :/>G: d:? 8/I C >Dd:<? / E>Dd:2</4?H C 4/d: >4&)? >4&2?

Jhere d: is the pore dia!eter >!?, < is the pore len'th >!?, : is the particle porosity, and G: is the particle density >'/!0?& Example 4.1 >a? Esti!ate the speci ic s%r ace area 8 o an adsorbent +ith : o 0&5, G: o ) '/c!0 >)06 '/!0?, and d: o 20K >2,)07)0 !?& >b? * the pore si(e increases to 2000K and #eep all other para!eters constant, +hat is the val%e o the speci ic s%r ace areaL >a?" )000 !2/' 5 >b?" )0 !2/'

8peci ic s%r ace area is typically deter!ined by AET correlation o /2 adsorption isother! at li$%id nitro'en te!perat%re& Metailed calc%lation !ethod +as disc%ssed in 8ection 2&4&2 >E$%ation 2&44?&

4&2&2

:ore vol%!e >c!0/'? *n characteri(in' the pore vol%!e, both total pore vol%!e and its distrib%tion over the

pore dia!eter are needed& The speci ic pore vol%!e, typically c!0 o pore vol%!e/' o adsorbent, is deter!ined or a s!all !ass o adsorbent, !adsorbent, by !eas%rin' the vol%!es o heli%!, I3e, and !erc%ry, I3', displaced by the adsorbent& The heli%! is not adsorbed, b%t ills the pores& At a!bient press%re, the !erc%ry cannot enter the pores beca%se o %n avorable inter acial tension and contact an'le& The speci ic pore vol%!e, is then deter!ined ro!"

Adsorption, ChE468/ChE568, Fall2005

IC >I3e 7 I3'?/!adsorbent C :/G:

>4&0?

Jhen adsorbents are %sed in a i,ed bed, the b%l# density b, or pac#in' density and bed porosity b are i!portant para!eters or adsorbents& *n addition, the tr%e solid density >also called crystalline density?, 8, can be calc%lated ro! the above para!eters& Aed porosity" :article porosity" :article density" Tr%e solid density" b C) N Gb/G: : C) N G:/Gs G: C !adsorbent /I3' Gs C !adsorbent /I3e >4&4? >4&5? >4&6? >4&9?

4&2&0

:ore si(e distrib%tion The pore si(e distrib%tion is !eas%red by !erc%ry porosi!etry or pores lar'er than )00

O)50 K and by /2 desorption >or adsorption? or pores in the ran'e )07250 K& For still s!aller pores, !olec%lar sievin' is %sed to deter!ine the si(e +hile the ad!itted sat%rated a!o%nt is %sed to deter!ine the pore vol%!e by %sin' the si!ple ;%rvitsch r%le, ass%!in' the pores are illed +ith li$%id& Mi erent !odels incl%din' -elvin e$%ation >AP3?, 3- approach, and inte'ral e$%ation approach have been %sed to calc%late pore si(e distrib%tion ro! adsorption data& Metails o these calc%lations can be o%nd in =& Qan's boo# RAdsorbent 77 F%nda!entals and ApplicationsS& Example 4.2 :oro%s particles o activated al%!ina have a AET s%r ace area o 0)0 !2/', a particle porosity o 0&48, and a particle density o )&00 '/c!0& Meter!ine" >a? speci ic pore vol%!e in c!0/' >b? tr%e solid density, '/c!0 and >c? appro,i!ate pore dia!eter in an'stro!s ro! >E$%ation 4&)?& Solution" >a?& Fro! E$%ation 4&0, I C :/G: C 0&48/)&00 C 0&06@ c!0/' >b?& Fro! e$%ation 4&5, : C) N G:/Gs, Gs C G:/>)7:? C )&00/>)70&48?C2&5 c!0/' >c?& Fro! e$%ation 4&), 8C4 :/>G: d:?, d:C 4:/>G: 8? C 4F0&48/>)&00,)06 F0)0? C5,)07@ ! C 50 K @

Adsorption, ChE468/ChE568, Fall2005

Example 4.3 Tsin' data ro! Table 4&2, deter!ine the vol%!e raction o pores in silica 'el >s!all7pore type? illed +ith adsorbed +ater vapor +hen its partial press%re is 4&6 !!3' and the te!perat%re is 25UC& At these conditions, the partial press%re is considerably belo+ the vapor press%re o 20&95 !!3'& *n addition, deter!ine +hether the a!o%nt o +ater adsorbed is e$%ivalent to !ore than a !onolayer, i the area o an adsorbed +ater !olec%le is 'iven by the ollo+in' e$%ation, and the speci ic s%r ace area o the silica 'el is 800 !2/'& C )&0@)>2//A<?2/0 +here" " s%r ace area covered per adsorbed !olec%le or close t+o7di!ensional pac#in' 2" !olec%lar +ei'ht o the adsorabte <" density o the adsorabte in '/c!0, ta#en as the li$%id at the adsorption te!perat%re& Solution: Ta#e ) ' o silica 'el particles as a basis& Fro! e$%ation 4&0 and data in Table 4&2, I C :/G: C 0&49/)&0@ >'/c!0? C 0&40) c!0/' Th%s, or ) ' o adsorbent, the pore vol%!e is 0&40) c!0& Fro! the capacity val%e in Table 4&2, a!o%nt o adsorbed +ater C 0&))/>) V 0&))? C 0&0@@) '& Ass%!e density o adsorbed +ater is ) '/c!0, vol%!e o adsorbed +ater C 0&0@@) c!0 raction o pores illed +ith +ater C 0&0@@)/0&40) C 0&200, and s%r ace area o ) ' C 800 !2 C )&0@)>2//A<?2/0 C )&0@)E)8&02/>6&020,)020?,)H2/0 C )&05),)07)5 c!2/!olec%le /%!ber o +ater !olec%les adsorbedC >0&0@@)?>6&020,)020?/)8&02C0&0),)02) !olec%els /%!ber o +ater !olec%les adsorbed in a !onolayer or 800 !2 C 800>)00?2/>)&05),)07)6?C9&@0,)02) !olec%les There ore, only 0&0)/9&@0 or 42W o one !onolayer is covered by the adsorbed +ater !olec%les&

)0

Adsorption, ChE468/ChE568, Fall2005

4.3

Ma or Commercial Adsorbents *n order to +ithstand the process environ!ent, co!!ercial adsorbents are %s%ally !an% act%red in 'ran%lar, spherical, or e,tr%ded or!s +ith si(es !ost o ten in the ran'e o 0&578 !!& 8pecial shapes as !onoliths or po+ers are !ade or special p%rposes& Fi'%re 5 displays the di erent shapes o the !ost co!!only !ade adsorbents in the !ar#et&
Fi'%re 4&5& Mi erent shapes o adsorbents

4&0&)

Activated carbon

Activated carbon is the !ost +idely %sed adsorbent& *ts !an% act%re and %se date bac# to the )@th cent%ry& *ts %se %lness derives !ainly ro! its lar'e !icropore and !esopore vol%!es and the res%ltin' hi'h s%r ace area& The pore si(e distrib%tion o a typical activated carbon is 'iven in Fi'%re 4&6, co!pared +ith several other co!!ercial adsorbents& The typical physical properties o activated carbon are 'iven in Table 4&0&

Fi'%re 4&6 Typical pore si(e distrib%tion o co!!ercial adsorbents

))

Adsorption, ChE468/ChE568, Fall2005

Table 4&0 Typical pore te,t%re properties o activated carbon

Preparation The !an% act%re and %se o activated carbon date bac# to the nineteenth cent%ry& The !odern !an% act%rin' processes basically involve the ollo+in' steps" ra+ !aterial preparation, pelleti(in', lo+7te!perat%re carboni(ation, and activation& The conditions are care %lly controlled to achieve the desired pore str%ct%re and !echanical stren'th& The ra+ !aterials or activated carbon are& carbonaceo%s !atters s%ch as +ood, peat, coals, petrole%! co#e, bones, cocon%t shell, and r%it n%ts& Anthracite and bit%!ino%s coals have been the !a1or so%rces& 8tartin' +ith the initial pores present in the ra+ !aterial, !ore pores, +ith desired si(e distrib%tions, are created by the so7called activation process& A ter initial treat!ent and pelleti(in', one activation process involves carboni(ation at 4007500UC to eli!inate the b%l# o the volatile !atter, and then partial 'asi ication at 8007)000UC to develop the porosity and s%r ace area& A !ild o,idi(in' 'as s%ch as C.2 strea!, or l%e 'as is %sed in the 'asi ication step beca%se the intrinsic s%r ace reaction rate is !%ch slo+er than the pore di %sion rate, thereby ens%rin' the %ni or! develop!ent o pores thro%'ho%t the pellet& The activation process is %s%ally per or!ed in i,ed beds, b%t in recent years l%idi(ed beds have also been %sed& The activated carbon created by the activation process is %sed pri!arily or 'as and vapor adsorption processes& The other activation process that is also %sed co!!ercially depends on the action o inor'anic additives to de'rade and dehydrate the cell%losic !aterials and, si!%ltaneo%sly, to prevent shrin#a'e d%rin' carboni(ation& This is called che!ical activation, %s%ally %sed or li'nin7based prec%rsors s%ch as sa+d%st&

)2

Adsorption, ChE468/ChE568, Fall2005

The activation step is cr%cial or tailorin' the pore si(e distrib%tion& This step is basically controlled 'asi ication, by %sin' stea!, C.2 or .2, as +ell as added catalysts& The 'asi ication reaction needs to be per or!ed in the #inetic controlled re'i!e, that is, %nder conditions +here the intrinsic reaction >rather than internal pore di %sion or e,ternal 'as il! di %sion? is the controllin' step& Adsorption Properties The %ni$%e s%r ace property o activated carbon, in contrast to the other !a1or adsorbents, is that its s%r ace is nonpolar or only sli'htly polar as a res%lt o the s%r ace o,ide 'ro%ps and inor'anic i!p%rities& This %ni$%e property 'ives activated carbon the ollo+in' advanta'es" )& *t is the only co!!ercial adsorbent %sed to per or! separation and p%ri ication processes +itho%t re$%irin' prior strin'ent !oist%re re!oval, s%ch as is needed in air p%ri ication& For the sa!e reason, it is also +idely %sed as an adsorbent or processes treatin' a$%eo%s sol%tions& 2& Aeca%se o its lar'e, accessible internal s%r ace >and lar'e pore vol%!e, sho+n in Fi'%re 4&6?, it adsorbs !ore nonpolar and +ea#ly polar or'anic !olec%les than other adsorbents do& For e,a!ple, the a!o%nt o !ethane adsorbed by activated carbon at ) at!osphere >at!? and roo! te!perat%re is appro,i!ately t+ice that adsorbed by an e$%al +ei'ht o !olec%lar sieve 5A >Fi'& 4&9?& 0& The heat o adsorption, or bond stren'th, is 'enerally lo+er on activated carbon than on other adsorbents& This is beca%se only non7speci ic, van der Jaals orces are available as the !ain orces or adsorption& Conse$%ently, strippin' o the adsorbed !olec%les is relatively east and res%lts in relatively lo+er ener'y re$%ire!ents or re'eneration o the adsorbent& *t is not correct, ho+ever, to re'ard activated carbon as hydrophobic& The e$%ilibri%! sorption o +ater vapor on an anthracite7derived activated carbon is co!pared +ith that o other adsorbents in Fi'%re 4&8& The adsorption o +ater on activated carbon ollo+s a Type I isother! +ith a 87shaped c%rve& The reason or the lo+ adsorption at lo+ vapor press%res is d%e to the lo+ van der Jaals interactions& .nce a e+ +ater !olec%les are adsorbed,

)0

Adsorption, ChE468/ChE568, Fall2005

adsorbate7adsorbatate interaction co!!ences, leadin' to cl%ster or!ation and event%ally pore illin' or capillary condensation in the !icropores& Activated carbon is %sed, nonetheless, in processes dealin' +ith h%!id 'as !i,t%res and +ater sol%tions beca%se the or'anic and nonpolar or +ea#ly polar co!po%nds adsorb !ore stron'ly, and hence pre erentially, on its s%r ace than +ater does&

Fi'%re 4&9& Adsorption isother!s o !ethane on di erent adsorbents at 25 C

Fi'%re 4&8 E$%ilibri%! adsorption o +ater ro! at!ospheric air on >A?& Al%!ina >'ran%lar?, >A? Al%!ina >spherical?, >C? 8ilica 'el, >M? 5A (eolite, >E? Activated carbon& The vapor press%re at )00W =3 is 20&6 torr&

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Adsorption, ChE468/ChE568, Fall2005

Carbon Molecular Sieve 8pecial !an% act%rin' proced%res can be %sed to !a#e a!orpho%s carbons +hich have a very narro+ distrib%tion o pore si(es +ith e ective dia!eters ran'in' ro! 0&470&@ n!& =a+ !aterials can be che!icals s%ch as polyvinylidene dichloride and phenolic resin, or nat%rally occ%rrin' !aterials s%ch as anthracite or hard coals& As sho+n in Fi'%re 4&@ the pore str%ct%re o activated carbons can be !odi ied to prod%ce a !olec%lar sieve carbon by coatin' the pore !o%ths +ith a carboni(ed or co#ed ther!osettin' poly!er& *n this +ay, 'ood #inetic properties !ay be obtained +hich create the desired selectivity, altho%'h the adsorptive capacity is so!e+hat lo+er than or activated carbons& The s%r ace is essentially non7polar and the !ain process application is the prod%ction o hi'h p%rity nitro'en ro! air by press%re s+in' adsorption&

Fi'%re 4&@ 2olec%lar sieve carbon !ade by A7F" >a?& C28 +ith bottlenec# o 0&5 n! or!ed by co#e deposition at the pore !o%th5 >b?& C28 or!ed by stea! activation CARBONIZED POLYMERS AND RESINS =esins s%ch as phenol or!aldehyde and hi'ly s%lphonated styrene/divinyl ben(ene !acroporo%s ion e,chan'e resins can be pyrolysed to prod%ce carbonaceo%s adsorbents +hich have !acro7, !eso7 and !icroporosity& 8%r ace areas !ay ran'e %p to ))00 !2/'& These adsorbents tend to be !ore hydrophobic than 'ran%lar activated carbon and there ore one i!portant application is the re!oval o or'anic co!po%nds ro! +ater&

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Adsorption, ChE468/ChE568, Fall2005

BONE C ARCOALS Ani!al bones can be carboni(ed to prod%ce adsorbent !aterials +hich have only !eso7 and !acropores and s%r ace areas aro%nd )00 !2/'& The pore develop!ent activation step %sed +ith activated carbons is dispensed +ith& The s%r ace is carbon and hydro,yl apatite in ro%'hly e$%al proportions and this d%al nat%re !eans that bone charcoals can be %sed to adsorb !etals as +ell as or'anic che!icals ro! a$%eo%s syste!s& Mecolo%ri(in' s%'ar syr%p is another application& 4&0&2 Activated Al%!ina

Activated al%!ina is a poro%s hi'h area or! o al%!ini%! o,ide +ith the or!%la Al2.0 n32.& *ts s%r ace is !ore polar than that o silica 'el and, re lectin' the a!photeric nat%re o al%!ini%!, has both acidic and basic characteristics& 8%r ace areas are in the ran'e 2507050 !2/'& Aeca%se activated al%!ina has a hi'her capacity or +ater than silica 'el at elevated te!perat%res it is %sed !ainly as a desiccant or +ar! 'ases incl%din' air b%t in !any co!!ercial applications it has no+ been replaced by (eolitic !aterials& ;ases or +hich activated al%!ina is s%itable incl%de ar'on, heli%!, hydro'en, lo+ !olec%lar +ei'ht al#anes >C)7C0?, chlorine, hydro'en chloride, s%lph%r dio,ide, a!!onia and l%oroal#anes& .ther %ses or activated al%!ina incl%de chro!ato'raphy and dryin' o li$%ids s%ch as #erosene, aro!atics, 'asoline ractions and chlorinated hydrocarbons& 4&0&0 8ilica ;el

8ilica 'el is a partially dehydrated poly!eric or! o colloidal silicic acid +ith the or!%la 8i.2 n32.& This a!orpho%s !aterial co!prises spherical particles 2720 n! in si(e +hich a''re'ate to or! the adsorbent +ith pore si(es in the ran'e 6725 n!& 8%r ace areas are in the ran'e )007850 !2/', dependin' on +hether the 'el is lo+ density or re'%lar density& The s%r ace co!prises !ainly 8i.3 and 8i.8i 'ro%ps and, bein' polar, it can be %sed to adsorb +ater, alcohols, phenols, a!ines, etc& by hydro'en bondin' !echanis!s& .ther co!!ercial applications incl%de the separation o aro!atics ro! para ins and the chro!ato'raphic separation o or'anic !olec%les&

)6

Adsorption, ChE468/ChE568, Fall2005

At lo+ te!perat%res the %lti!ate capacity o silica 'el or +ater is hi'her than the capacity on al%!ina or (eolites& At lo+ h%!idity, ho+ever, the capacity o silica 'el or !oist%re is less than that o a (eolitic desiccant& .n the other hand, silica 'el is !ore easily re'enerated by heatin' to )50 C than (eolitic !aterials +hich need to be heated to abo%t 050 C& 8ilica 'el there ore tends to be %sed or dryin' applications in +hich hi'h capacity is re$%ired at lo+ te!perat%re and !oderate +ater vapo%r press%res& The heat o adsorption o +ater vapor is abo%t 45 #P/!ol& 8ilica 'el !ay lose activity thro%'h poly!eri(ation +hich involves the s%r ace hydro,yl 'ro%ps& Typical properties o adsorbent 'rade silica 'el are s%!!ari(ed in Table 4&4& Fi'%re 4&4 Typical properties o adsorbent 'rade silica 'el

4&0&4

6eolites

6eolites are poro%s crystalline al%!inosilicates +hich co!prise asse!blies o 8i.4 and Al.4 tetrahedra 1oined to'ether thro%'h the sharin' o o,y'en ato!s& 2ore than )50 synthetic (eolite types are #no+n, the !ost i!portant co!!ercially bein' the synthetic types A and X, synthetic !ordenite and their ion7e,chan'ed varieties& . the 40 or so !ineral (eolites the !ost i!portant co!!ercially are chaba(ite, a%1asite and !ordenite& Cavities >or ca'es? are contained +ithin the ra!e+or# o a (eolite and are connected by re'%lar channels >pores? +hich are o !olec%lar di!ensions and into +hich adsorbate !olec%les can penetrate& *n crystal or!, (eolites are distinct ro! other adsorbents in that, or each type,

)9

Adsorption, ChE468/ChE568, Fall2005

there is no distrib%tion o pore si(e beca%se the crystal lattice into +hich the adsorbate !olec%les can or cannot enter is precisely %ni or!& The internal porosity is hi'h and th%s the !a1ority o adsorption ta#es place internally& For this reason (eolites are capable o separatin' e ectively on the basis o si(e and they have been assi'ned the pop%lar description o !olec%lar sieves& The processes o adsorption and desorption o !olec%les in (eolites are based on di erences in !olec%lar si(e, shape and other properties s%ch as polarity& For physical adsorption the cavities ill and e!pty reversibly and the !echanis! is 'enerally considered to be one o pore illin'& 3ence the s%r ace area concepts presented or other types o adsorbent strictly do not apply& The channel si(e is deter!ined by the n%!ber o ato!s +hich or! the apert%res >or +indo+s? leadin' to the ca'es& For e,a!ple, apert%res !ay be constr%cted ro! rin's o 6, 8, )0 or )2 o,y'en ato!s to'ether +ith the sa!e n%!ber o al%!ini%! and/or silicon ato!s& Ca'es or!ed +ith 6 o,y'en ato! apert%res can ad!it only the s!allest !olec%les s%ch as +ater and a!!onia& 6eolites containin' 8, )0 and )2 o,y'en ato! rin's have li!itin' apert%re si(es o 0&42, 0&59 and 0&94 n!, respectively, and are penetrable by !olec%les o increasin' si(e& *t is possible or !olec%les sli'htly lar'er than the apert%re si(e to 'ain access to the cavities beca%se o the vibration o !olec%les and o the crystal lattice& Fi'%re 4&)0 sho+s a sche!atic representation o the ra!e+or# str%ct%re o (eolite A and the a%1asite analo'%es X and Q& A %ller introd%ction to the str%ct%res o di erent (eolite types is provided by =%thven >)@84?& The e!pirical or!%la o a (eolite ra!e+or# is 22/n&Al2.0&,8i.2&y32. +here , is 'reater than or e$%al to 2, n is the cation valency and y represents the +ater contained in the cavities& The +ater can be reversibly re!oved by heatin' leavin' a !icroporo%s str%ct%re +hich !ay acco%nt or %p to 50W o the crystals by vol%!e& The ratio o o,y'en ato!s to co!bined silicon and al%!ini%! ato!s is al+ays e$%al to t+o and there ore each al%!ini%! ato! introd%ces a ne'ative char'e on the (eolite ra!e+or# +hich is balanced by that o an e,chan'eable cation& Chan'in' the position and type o the cation chan'es the channel si(e and properties o the (eolite, incl%din' its selectivity in a 'iven che!ical syste!& The positions occ%pied by cations in a ra!e+or# depend on the n%!ber o cations per %nit cell&

)8

Adsorption, ChE468/ChE568, Fall2005

Considerin' type A (eolite as an e,a!ple, all cations can be acco!!odated at sites +ithin the ca'es i Ca 2V is the cation& =eplacin' Ca 2V by /aV increases the n%!ber o cations per %nit cell& *n this case the additional cations are acco!!odated in sites +ithin the ei'ht rin's o the apert%res so that the +indo+s beco!e partially obstr%cted and the channel si(e is red%ced to 0&08 n!& * the Ca 2V is replaced by -V then the lar'er cation red%ces the channel si(e even %rther to 0&0 n!&

Fi'%re )0& 8che!atic representation sho+in' the ra!e+or# str%ct%re o >a? (eolite A and >b? (eolite X and Q *n addition to chan'es to the cationic str%ct%re, the 8i/Al ratio can be varied d%rin' !an% act%re ro! %nity to +ell over )000& Th%s (eolites +ith +idely di erent adsorptive properties !ay be tailored by the appropriate choice o ra!e+or# str%ct%re, cationic or! and silica to al%!ina ratio in order to achieve the selectivity re$%ired or a 'iven separation& 2any (eolites are e,tre!ely polar and there ore separations !ay be e ected %sin' both !olec%lar sievin' and internal s%r ace property e ects& The #inetic selectivity is deter!ined ro! the ree dia!eters o the +indo+s in the intra7crystalline channel str%ct%re& E,a!ples o s%ch dia!eters, to'ether +ith the principal properties and !ain %ses o (eolites, are 'iven in Table 4&5& 4&0&5 :oly!eric Adsorbents

A broad ran'e o synthetic, non7ionic poly!ers is available partic%larly or analytical chro!ato'raphy applications& For preparative and ind%strial %ses, co!!ercially available resins in bead or! >typically 0&5 !! dia!eter ? are based %s%ally on co7poly!ers o

)@

Adsorption, ChE468/ChE568, Fall2005

styrene/divinyl ben(ene and acrylic acid esters/divinyl ben(ene and have a ran'e o s%r ace polarities& The relevant !ono!ers are e!%lsion poly!eri(ed in the presence o a solvent +hich dissolves the !ono!ers b%t +hich is a poor s+ellin' a'ent or the poly!er& This creates the poly!er !atri,& 8%r ace areas !ay ran'e %p to 950 !2/'& Table 4&5 8o!e i!portant applications o (eolite adsorbents

8elective adsorption properties are obtained ro! the str%ct%re, controlled distrib%tion o pore si(es, hi'h s%r ace areas and che!ical nat%re o the !atri,& Applications incl%de the recovery o a +ide ran'e o sol%tes ro! the a$%eo%s phase, incl%din' phenol, ben(ene, tol%ene, chlorinated or'anics, :CAs, pesticides, antibiotics, acetone, ethanol, deter'ents, e!%lsi iers, dyes, steroids, a!ino acids, etc& =e'eneration !ay be e ected by a variety o

20

Adsorption, ChE468/ChE568, Fall2005

!ethods +hich incl%de stea! desorption, solvent el%tion, p3 chan'e and che!ical e,traction& The ionic nat%re o !ost (eolites !eans that they have a hi'h a inity or +ater and other polar !olec%les s%ch as carbon dio,ide and hydro'en s%lphide& 3o+ever, as the silica7to7 al%!ina ratio is increased the !aterial can beco!e hydrophobic& 8ilicalite, a pentasil (eolite, e ectively contains no al%!ini%! and, as +ith de7al%!ini(ed Q7type (eolite, can be %sed to re!ove hydrocarbons ro! a$%eo%s syste!s and ro! h%!id 'ases& They there ore ind applications in the re!oval o volatile or'anic co!po%nds ro! air& As an alternative to activated carbons hi'h silica (eolites have several advanta'es& First, they can be %sed at relatively hi'h h%!idities& Carbons ta#e %p appreciable $%antities o !oist%re at hi'h h%!idity thereby li!itin' their e ectiveness or I.C control& 8econdly, (eolites are inor'anic and hence they can be re'enerated in air, s%b1ect to la!!ability considerations& Thirdly, hi'h silica (eolites do not sho+ catalytic activity and proble!s o heatin' +ith #etones do not arise as +ith carbons& Co!!ercially available synthetic (eolites are 'enerally prod%ced via the ollo+in' se$%ence o steps" synthesis, pelleti(ation and calcination& 8ynthesis is carried o%t %nder hydrother!al conditions, i&e& crystalli(ation ro! a$%eo%s syste!s containin' vario%s types o reactant& ;els are crystalli(ed in closed syste!s at te!perat%res +hich vary bet+een roo! te!perat%re and 200UC& The ti!e re$%ired !ay vary ro! a e+ ho%rs to several days& The crystals are iltered, +ashed, ion e,chan'ed >i re$%ired? and then !i,ed +ith a s%itable clay binder& The pellets are then or!ed, %s%ally as spheres or e,tr%dates be ore bein' dried and ired to provide the inal prod%ct& The binder !%st provide the !a,i!%! resistance to attrition +hile acilitatin' the di %sion o adsorbates into the !icroporo%s interior& 4.4 Selection o! Adsorbents The selection o a proper adsorbent or a 'iven separation is a co!ple, proble!& The predo!inant scienti ic basis or adsorbent selection is the e$%ilibri%! isother!& Mi %sion rate is 'enerally secondary in i!portance& The e$%ilibri%! isother!s o all constit%ents in the 'as !i,t%re, in the press%re and te!perat%re ran'e o operation, !%st be considered& As a irst and oversi!pli ied appro,i!ation, the p%re7'as isother!s !ay be considered additive to 2)

Adsorption, ChE468/ChE568, Fall2005

yield the adsorption ro! a !i,t%re& 2odels and theories or calc%latin' !i,ed 'as adsorption sho%ld be %sed to provide better esti!ates or e$%ilibri%! adsorption& Aased on the isother!s, the ollo+in' actors that are i!portant to the desi'n o the separation process can be esti!ated" )& Capacity o the adsorbent, in the operatin' te!perat%re and press%re ran'e& 2& The !ethod o adsorbent re'eneration 7 or e,a!ple, te!perat%re or press%re s+in'7 and the !a'nit%de o the re$%ired s+in'& 0& The len'th o the %n%sable >or %n%sed? bed ><TA?& 4& The prod%ct p%rities& The <TA is appro,i!ately one7hal the span o the concentration +ave ront, or the !ass trans er (one& The <TA is pri!arily deter!ined by the e$%ilibri%! isother!& A sharp concentration ront, or a short <TA, is desired beca%se it res%lts in a hi'h adsorbent prod%ctivity as +ell as hi'h prod%ct p%rity& The property +hich is !ost co!!only st%died initially is the e$%ilibri%! isother!>s? or the che!ical syste! to be separated or p%ri ied& E$%ilibri%! data is re$%ired or the te!perat%re and press%re ran'es o interest and !%st be obtained e,peri!entally i it is not available ro! the adsorbent vendor& *sother!s or the p%re species provide an indication o the s%itability o an adsorbent or a partic%lar separation b%t care needs to be ta#en +hen interpretin' in or!ation +hen !ore than one species is to be adsorbed& * the e$%ilibri%! data indicates that an adsorbent !i'ht be s%itable or the desired separation then it is necessary to deter!ine +hether the #inetic properties are appropriate& Even tho%'h !ost separations are e ected beca%se o the e$%ilibri%! e ect it is still necessary to ens%re that the rate o %pta#e o the adsorbates is s%itable and that the appropriate p%rities can be achieved& A'ain reco%rse !ay need to be 'iven to e,peri!entation i the adsorbent vendor cannot s%pply the #inetic in or!ation& ;iven that the e$%ilibria and #inetics o adsorption are appropriate, consideration !%st ne,t be 'iven to the !eans by +hich the adsorbent is 'oin' to be re'enerated, i it is not to be

22

Adsorption, ChE468/ChE568, Fall2005

discarded a ter %se& Mependin' on the process application, re'eneration can be e ected by chan'in' the press%re and/or the te!perat%re or by so!e other physical or che!ical alteration to the syste!& Consideration !%st also be 'iven to actors s%ch as the stren'th o the adsorbent, its che!ical resistance, its resistance to co#in', etc&, as +ell as to its availability and price& Finally, Table 4&6 lists typical applications o co!!on types o adsorbent& Consideration sho%ld also be 'iven to other actors& Activated carbon is the only !a1or co!!ercial adsorbent %sed or +et 'as strea! processin'& >A pre7dryer is re$%ired or other adsorbents&? Adsorbent deactivation, pri!arily by co#e deposition, is an i!portant consideration in the processin' o hydrocarbon containin' 'ases& Co#e is or!ed catalytically, and (eolites are e,cellent catalysts or these reactions d%e to their acidities& :ore7si(e distrib%tion can play a role in the <TA, b%t not as i!portant as the e$%ilibri%! isother!, since the co!!ercial adsorbent pellets are desi'ned to !ini!i(e the pore7di %sion resistance& -inetic separation that is, separation based on the di erence bet+een pore di %sivities o t+o 'ases, has o%nd only one !a1or application" the prod%ction o nitro'en ro! air by !olec%lar sieve carbon& Mehydration o crac#ed 'ases +ith 0A (eolite and the separation o nor!al and iso7para ins +ith 5A (eolite are based on selective !olec%lar e,cl%sion& All other co!!ercial processes are based on the e$%ilibri%! isother!s& Te!perat%re or activation and re'eneration o the adsorbent sho%ld also be considered& A hi'h te!perat%re >in the 000UC ran'e? is re$%ired or (eolites, +hereas activated carbon %s%ally re$%ires the lo+est te!perat%re or re'eneration& The total void space in the bed, +hich varies +ith the adsorbents, is also an i!portant actor& A lo+ void space is desired or hi'h prod%ct recoveries beca%se the 'as !i,t%re re!ainin' in the void space o the sat%rated bed is %s%ally not recovered as a %se %l prod%ct& 8ilica 'el and activated al%!ina have the lo+est void ractions, %s%ally sli'htly belo+ 90W& Activated carbon has the hi'hest void raction, at nearly 80W&

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Adsorption, ChE468/ChE568, Fall2005

Table 4&6 8elected Applications o Co!!ercial Adsorbents

24

Adsorption, ChE468/ChE568, Fall2005

25

Adsorption, ChE468/ChE568, Fall2005

A%l# separation re ers to separation o a !i,t%re that contains over appro,i!ately )0W in concentration or the co!ponent to be adsorbed& Adsorbent selection depends on the nat%re o the separation >i&e&, b%l# separation vs& p%ri ication? as +ell as the process by +hich the separation +ill be acco!plished >i&e&, press%re s+in' vs& te!perat%re s+in'?& As !entioned, the !ost i!portant basis or adsorbent selection is the e$%ilibri%! isother!, +hile di %sivity is a secondary actor or consideration& 4." #e$ Adsorbent Materials *n the develop!ent o ne+ ener'y technolo'ies, s%ch as %el cells, adsorption can play a #ey enablin' role& A brea#thro%'h in adsorbent develop!ent is needed to solve the critical proble! o hydro'en stora'e or hydro'en %el cells& The best %el or %el cells is 'asoline >beca%se o its hi'h7ener'y density, ready availability, and sa ety in handlin'?& 3o+ever, to avoid poisonin' o the :t catalyst in the %el cell, the s%l %r content in 'asoline needs to be 26

Adsorption, ChE468/ChE568, Fall2005

red%ced ro! the present level o 050 pp! to Y) pp!& These challen'es cannot be !et +ith the adsorbents that are c%rrently available& F%t%re needs or a clean environ!ent +ill lead to increasin'ly hi'her standards or air and +ater poll%tants& These challen'es re$%ire better adsorbents that are not co!!ercially available& Traditionally, adsorbents +ere developed based on e!piricis!& To !eet the ne+ challen'es, tailored adsorbents need to be developed based on %nda!ental principles& Theoretical tools, s%ch as ab initio !olec%lar orbital theory and 2onte Carlo si!%lations can be %sed to speed %p the adsorbent desi'n& *t is one o the 'oals o this boo# to help p%t adsorbent desi'n on a !ore rational basis& 8o!e o the !ost challen'in' proble!s in separation and p%ri ication that re$%ire ne+ adsorbents are 'iven in Table 4&9& /e+ adsorbents that can solve these proble!s are also 'iven& F%rther innovations are needed or !eetin' these and !any !ore %t%re challen'es&

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Adsorption, ChE468/ChE568, Fall2005

Table 4&9 F%t%re 8eparation and :%ri ication Applications by /e+ Adsorbents

28