AdsorpLlon phenomenon and

adsorbenL MaLerlals
resenLed 8y
Pemang Muar[l
8oll no13
3
rd
SemesLer
MScMaLerlals Sclence
onLenL
AdsorpLlon henomenon
W lnLroducLlon
W 1ypes of adsorpLlon
W AdsorpLlon of gas by solld
W AppllcaLlon of AdsorpLlon
AdsorbenL
W Molecular sleves
W AcLlvaLed arbon
W ZeollLes
W Slllca gel
W ressure swlng adsorpLlon
W 8eferences
lnLroducLlon
Adsorpt|on AdsorpLlon Laklng up of a gas or llquld aL Lhe surface of
anoLher subsLance mosL commonly a solld (eg acLlvaLed carbon zeollLe
eLc lL lnvolves molecular aLLracLlon aL Lhe surface and lL should
dlsLlngulshed from absorpLlon
AdsorpLlon lmplles concenLraLlon aL Lhe surface only and AbsorpLlon
lmplles LhaL a subsLance ls unlformly dlsLrlbuLlon LhroughouL Lhe body of
a solld or a llquld
Lg Ammonla ls absorb ln waLer lL ls adsorb by charcoalWaLer vapor are
absorb by anhydrous calclum chlorlde Lhese are adsorbed by slllca gel
1here are two pr|nc|pa| modes of adsorpt|on
of mo|ecu|es on surfaces
hys|ca| adsorpt|on 1hls ls due Lo gas
molecule belng held Lo Lhe solld surface by
van dar waal's aLLracLlve forces eg
adsorpLlon of hydrogen and oxygen on a
charcoal ls physlcal adsorpLlon
Chem|sorpt|on 1he gas and llquld
molecules are held on solld surface of
(adsorbenL) by chemlcal bond eg
Pydrogen molecule ls chemlsorbed on
nlckel
Compar|son of hys|ca| adsorpt|on and
Chem|sorpt|on
W aused by lnLermolecular van der
waal's forces
W 8everslble
W PeaL of adsorpLlon ls small (abouL
340 k! mol
1
)
W Cccurs rapldly aL low
LemperaLure decrease wlLh
lncreaslng LemperaLure
W lncrease of pressure lncrease
adsorpLlon decrease of pressure
causes desorpLlon
W lormaLlon of mulLllayer on
adsorbenL surface
W aused by chemlcal bond
formaLlon
W lrreverslble
W PeaL of adsorpLlon ls large (40
800 k! mol
1
)
W lncrease wlLh lncrease of
LemperaLure
W hange of pressure has no such
effecL
W lorms unlmolecular layer
Jhen Gas Mo|ecu|es Get Stuck on Surfaces "
Jhen a gas mo|ecu|e h|ts a surface severa| th|ngs
may happen
W lL may be reflecLed
W lL may blnd Lo Lhe surface remalnlng lnLacL as a
molecule (molecolot oJsotptloo) or lL may dlssoclaLe
and lLs fragmenLs (eg Lhe aLoms lL conslsLs of) blnd Lo
Lhe surface (Jlssoclotlve oJsotptloo)
W ln a few speclal cases gas molecules can dlssoclaLe as
Lhey hlL a surface and only parL of Lhe fragmenLs
remaln on Lhe surface and parL of Lhe molecule ls
absLracLed le leaves Lhe surface (obsttoctlve
oJsotptloo)
AdsorpLlon of gas by sollds
1he adsorpLlon of gases adsorbenL has cerLaln characLerlsLlc
feaLures
Adsorpt|on and surface area AdsorpLlon belng a surface
phenomenon Lhe exLenL of adsorpLlon ls depends on Lhe
surface area lncrease ln Lhe surface area of Lhe adsorbenL
lncreases Lhe LoLal amounL of Lhe gas adsorbed 1hus flnely
dlvlded meLals (nlckel laLlnum) and porous subsLances
(harcol Slllca gel) rovlde a large surface area and are besL
solld adsorbenLs
kevers|b|e character hyslcal adsorpLlon ls a reverslble
process 1he gas adsorbed lnLo a solld can be removed under
reverse condlLlons of LemperaLure and pressure ln oLher way
chemlsorpLlon ls noL reverslble because of chemlcal bond
formed beLween gas molecules and solld surface
ffect of 1emperature hyslcal adsorpLlon occurs rapldly aL low
LemperaLure and decrease wlLh lncreaslng LemperaLure When chemlsorpLlons
lncreases wlLh lncreases of LemperaLure
eg nlLrogen ls physlcally adsorbed on lorn aL 190 buL chemlsorbed Lo form a
nlLrlde aL 300
neat of adsorpt|on PeaL of adsorpLlon ls deflned as Lhe energy llberaLed
When 1 mole of a gas ls adsorbed on Lhe solld surface ln physlcal adsorpLlon gas
molecules concenLraLe on Lhe solld surface 1hus lL ls slmllar Lo Lhe condensaLlon of
a gas Lo llquld 1herefore adsorpLlon llke condensaLlon ls an exoLhermlc process 1he
aLLracLlon beLween gas molecule and solld surface (adsorbenL) are due Lo relaLlvely
weak van der waal's force PeaL of adsorpLlon ls very small (abouL 340 k! mol
1
) ln
hemlsorpLlon Lhe aLLracLlve forces are due Lo Lhe formaLlon of hemlcal bonds
1herefore Lhe heaLs of adsorpLlonare large (40 800 k! mol
1
)
ffect of pressure lL has been found LhaL lncreases of pressure leads Lo
lncreases of adsorpLlon and decreases of pressure cause desorpLlon
W
ALlA1lCn Cl AuSC81lCn
W lor producLlon of hlgh vacuum
W 8emoval of colourlng meLal from soluLlon
W lor preparlng gas mask
W lndusLrlal recovery of vapours
W SeparaLlon of gas mlxLures
W lor reflnlng peLroleum and vegeLable olls
W Slllca and alumlna gel are used as adsorbenLs for removlng molsLure and for
conLrolllng humldlLy
W lroLh floLaLlon process
W hromaLographlc Analysls
Mo|ecu|ar s|eve
A mo|ecu|ar s|eve ls a maLerlal conLalnlng Llny pores of a preclse and unlform
slze LhaL ls used as an adsorbenL for gases and llqulds
Molecules small enough Lo pass Lhrough Lhe pores are adsorbed whlle larger
molecules are noL lL ls dlfferenL from a common fllLer ln LhaL lL operaLes on a
molecular level lor lnsLance a waLer molecule may be small enough Lo pass
Lhrough whlle larger molecules are noL 8ecause of Lhls Lhey ofLen funcLlon as a
deslccanL A molecular sleve can adsorb waLer up Lo 22 of lLs own welghL
CfLen Lhey conslsL of alumlnoslllcaLe mlnerals clays porous glasses
mlcroporous charcoals zeollLes acLlve carbons or synLheLlc compounds LhaL
have open sLrucLures Lhrough whlch small molecules such as nlLrogen and
waLer can dlffuse
Molecular sleves are ofLen uLlllzed ln Lhe peLroleum lndusLry especlally for Lhe
purlflcaLlon of gas sLreams and ln Lhe chemlsLry laboraLory for separaLlng
compounds and drylng reacLlon sLarLlng maLerlals
MeLhods for regeneraLlon of molecular sleves lnclude pressure change (as ln
oxygen concenLraLors) heaLlng and purglng wlLh a carrler gas (as when used ln
eLhanol dehydraLlon) or heaLlng under hlgh vacuum
Act|vated carbon
Act|vated carbon |s a h|gh|y porous amorphous so||d cons|st|ng of
m|crocrysta|||tes w|th a graph|te |att|ce usua||y prepared |n sma|| pe||ets or a
powder Act|vated carbon can be manufactured from carbonaceous mater|a|
|nc|ud|ng coa| (b|tum|nous subb|tum|nous and ||gn|te) peat wood or
nutshe||s (|e coconut) 1he manufactur|ng process cons|sts of two phases
carbon|zat|on and act|vat|on 1he carbon|zat|on process |nc|udes dry|ng and
then heat|ng to separate byproducts |nc|ud|ng tars and other hydrocarbons
from the raw mater|a| as we|| as to dr|ve off any gases generated 1he
carbon|zat|on process |s comp|eted by heat|ng the mater|a| at 400600 C |n an
oxygendef|c|ent atmosphere that cannot support combust|on
W 1he carbon|zed part|c|es are "act|vated" by expos|ng them to
an ox|d|z|ng agent usua||y steam or carbon d|ox|de at h|gh
temperature 1h|s agent burns off the pore b|ock|ng
structures created dur|ng the carbon|zat|on phase and so
they deve|op a porous threed|mens|ona| graph|te |att|ce
structure 1he s|ze of the pores deve|oped dur|ng act|vat|on
|s a funct|on of the t|me that they spend |n th|s stage Longer
exposure t|mes resu|t |n |arger pore s|zes 1he most popu|ar
aqueous phase carbons are b|tum|nous based because of
the|r hardness abras|on res|stance pore s|ze d|str|but|on
and |ow cost but the|r effect|veness needs to be tested |n
each app||cat|on to determ|ne the opt|ma| product
W Act|vated carbon |s used for adsorpt|on of organ|c
substances and nonpo|ar adsorbates and |t |s a|so usua||y
used for waste gas (and waste water) treatment It |s the
most w|de|y used adsorbent Its usefu|ness der|ves ma|n|y
from |ts |arge m|cropore and mesopore vo|umes and the
resu|t|ng h|gh surface area
eo||tes
ZeollLes are naLural or synLheLlc crysLalllne alumlnoslllcaLes whlch have
a repeaLlng pore neLwork and release waLer aL hlgh LemperaLure
ZeollLes are polar ln naLure
1hey are manufacLured by hydroLhermal synLhesls of sodlum
alumlnoslllcaLe or anoLher slllca source ln an auLoclave followed by lon
exchange wlLh cerLaln caLlons (na
+
Ll
+
a
2+
k
+
nP
4
+
) 1he channel
dlameLer of zeollLe cages usually ranges from 2 Lo 9 1he lon
exchange process ls followed by drylng of Lhe crysLals whlch can be
pelleLlzed wlLh a blnder Lo form macroporous pelleLs
ZeollLes are applled ln drylng of process alr C
2
removal from naLural
gas C removal from reformlng gas alr separaLlon caLalyLlc cracklng
and caLalyLlc synLhesls and reformlng
nonpolar (slllceous) zeollLes are synLheslzed from alumlnumfree
slllca sources or by dealumlnaLlon of alumlnumconLalnlng zeollLes
1he dealumlnaLlon process ls done by LreaLlng Lhe zeollLe wlLh sLeam
aL elevaLed LemperaLures Lyplcally greaLer Lhan 300 (1000 l) 1hls
hlgh LemperaLure heaL LreaLmenL breaks Lhe alumlnumoxygen bnds
and Lhe alumlnum aLom ls expelled from Lhe zeollLe framework
S|||ca ge|
8eads of s|||ca ge|
S|||ca ge| ls a granular porous form of slllca made synLheLlcally from
sodlum slllcaLe uesplLe Lhe name slllca gel ls a solld
Slllca gel ls mosL commonly encounLered ln everyday llfe as beads
packed ln a semlpermeable plasLlc ln Lhls form lL ls used as a
deslccanL Lo conLrol local humldlLy ln order Lo avold spollage of some
goods 8ecause of polsonous dopanLs and Lhelr very hlgh adsorpLlon
of molsLure slllca gel packeLs usually bear warnlngs for Lhe user noL Lo
eaL Lhe conLenLs lf consumed Lhe pure slllca gel ls unllkely Lo cause
acuLe or chronlc lllness buL would be problemaLlc noneLheless
Powever some packaged deslccanLs may lnclude funglclde and/or
pesLlclde polsons
8eads of slllca gel 8eads of slllca gel
loodgrade deslccanL should noL lnclude any polsons
whlch would cause longLerm harm Lo humans lf
consumed ln Lhe quanLlLles normally lncluded wlLh Lhe
lLems of food
Slllca gels hlgh surface area (around 800 m/g)
allows lL Lo absorb waLer readlly maklng lL useful as a
deslccanL (drylng agenL) Cnce saLuraLed wlLh waLer
Lhe gel can be regeneraLed by heaLlng Lo 120
(230 l) for Lwo hours Some Lypes of slllca gel wlll
pop when exposed Lo enough waLer
ressure sw|ng adsorpt|on
W ressure Sw|ng Adsorpt|on (SA) |s a techno|ogy used to
separate some gas spec|es from a m|xture of gases under
pressure accord|ng to the spec|es mo|ecu|ar character|st|cs
and aff|n|ty for an adsorbent mater|a| It operates at near
amb|ent temperatures and so d|ffers from cryogen|c
d|st|||at|on techn|ques of gas separat|on Spec|a| adsorpt|ve
mater|a|s (eg zeo||tes) are used as a mo|ecu|ar s|eve
preferent|a||y adsorb|ng the target gas spec|es at h|gh
pressure 1he process then sw|ngs to |ow pressure to desorb
the adsorbent mater|a|
W Us|ng two adsorbent vesse|s a||ows nearcont|nuous
product|on of the target gas It a|so perm|ts soca||ed
pressure equa||sat|on where the gas |eav|ng the vesse|
be|ng depressured |s used to part|a||y pressur|se the second
vesse| 1h|s resu|ts |n s|gn|f|cant energy sav|ngs and |s
common |ndustr|a| pract|ce
App||cat|ons of the SA techno|ogy
W Cne of the pr|mary app||cat|ons of SA |s |n the remova| of carbon
d|ox|de (CC
2
) as the f|na| step |n the |argesca|e commerc|a|
synthes|s of hydrogen (n
2
) for use |n o|| ref|ner|es and |n the
product|on of ammon|a (Nn
3
) kef|ner|es often use SA
techno|ogy |n the remova| of hydrogen su|f|de (n
2
S) from
hydrogen feed and recyc|e streams of hydroteat|ng and
hydrocrack|ng un|ts Another app||cat|on of SA |s the separat|on
of carbon d|ox|de from b|ogas to |ncrease the methane (Cn
4
)
content 1hrough SA the b|ogas can be upgraded to a qua||ty
s|m||ar to natura| gas
W kesearch |s current|y underway for SA to capture CC
2
|n |arge
quant|t|es from coa|f|red power p|ants pr|or to reduce
greenhouse gas product|on from these p|ants
SA |s an econom|c cho|ce for sma||sca|e product|on of
reasonab|e pur|ty oxygen or n|trogen from a|r SA
techno|ogy has a ma[or use |n the med|ca| |ndustry to
produce oxygen part|cu|ar|y |n remote or |naccess|b|e parts
of the wor|d where bu|k cryogen|c or compressed cy||nder
storage are not poss|b|e
SA has a|so been d|scussed as a future a|ternat|ve to the
nonregenerab|e sorbent techno|ogy used |n space su|t
r|mary L|fe Support Systems |n order to save we|ght and
extend the operat|ng t|me of the su|t
8LlL8LnLS
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