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16                                    PRloSSLIRE SWING ADSORPTION                FUNDAMENTALS OF ADSORPTION                                    17

                                                                                                distribution of pore size. This unifornutv of pore size 1s  achieved in  two wavs:
                           (d)
                                                                                                by  careful  control  of  the  conditions  ctunng  the  act1vat1on  step  and  by
                    .OlS                                                                        controlled ctepos1t1on of easily crackable or oolvmenzable  hvctrocarbons such
                                                                                                as  acetylene.  Control  of  these  processes  provides  the  means  by  which  the
                                                                                                pore  size  can  be  adjusted.s.ei  In  this  resoect  there  1s  somewhat  greater
                                                                                                flexibility  than  with  crystalline  m1crooorous  materiais  rn  which  the  oore
                                                                                                dimensions  are  fixed  bY  the  ccystai  structure.  ln  kinetically  selective  adsor-
              Por<>  Vol •• 0\0
                                                                                                bents  the  onmary  parameters  deterrnmmg  the  sel'ect1v1tv  are  the  pore  size
                                               \                                                secondary  importance.  Thus,  desmte  the  difference  m  chem1ca1  nature,
                                                                                                and  pore  size  distribution.  The  nature  of  the  :matenal  1s  generally  of
                    . oos                                                                       small-oore  zeolites  and  molecular  sieve  carbons  exhibit  very  s11Tlilar  kinetic
                                                \                                               selectivities.
                                                 I
                                                 \
                                                  ~                                               2.1.5  Phystcal  Strength
                                ..
                   O. 000  __.__........,...Lu .;..o.L....__._   .u.J ___ ,_,___._J...,.......,~, ....
                      ,001      .Ol                                                             Reoeated  pressurization  and  deoressunzat1on  of an  adsorbent  bed  tends  to
                                       Poro  Olom.ilor  '()'  (M!crona)                         cause  attrition  of  the  adsorbent  particles.  Physical  strength  1s  therefore  a
                Figure 2.2  (d). Pore size distrihut1on for  pelleted SA i.colitc (only the cxtracrystallinc   pnme  consideration  m  the  ct101cc  of an  adsorhcnt  for  a  PSA  procc,;s.  Such
                pores arc shown).                                                               considerat10ns may  mdeed  preclude  the use of an  otherwise  des,rablc adsor•
                                                                                                bent m  favor  of a matenal  that,  from  kinetic and  eauilibnum considerations
                                                                                                aione. may appear to have mferior properties. Both the "crush strength" and
                determined  by  the  crystal  structure.  Some  control  of  pore  size  can  be
                                                                                                the  "abrasion  resistance"  are  strongly  deoenctent  on  the  way  in  which  the
                achieved  by  procedures  such  as  silanat1on  and  by  10n  exchange,  smce,  m
                                                                                                adsorbent oart1cles are manufactured, mcluding such factors  as the nature of
                many  zeolites,  the  cations  partially  (or  even  totallv)  obstruct  the  mtracrys-
                                                                                                the binder and the pretreatment conditions, but only very limited infonnatton
                talline microoores."'  By  contrast,  the carbon  molecular sieves are amorphous
                                                                                                1s  available in  the open literature.*
                matenals  similar  to  high-area  activated  carbons  but  with  a  much  narrower
                                                                                                   2.1.6  Activated Carbon and Carbon Molecular Sieves
                Table 2.2.  Classification of Comrnerc1al Adsorbents
                                                                                                 Activated  carbon  is  produced  m  many  different  forms  that  differ  mamiy  m
                         Equilibrmm selective            Kinet1cally selective
                                                                                                 pore  size  distribution  and  surface  polarity.  The  nature  of  the  final  product
                    Hydrophilic    Hydrophobic     Amorphous       Crv.~talline
                                                                                                 depends  on  both  the  starting  material  and  the  aci1vat1on  proccclurc.  For
                  Activated alumina   Activated carbon   Carbon molecular   Small-pore zeoli1es   liquid-phase  adsorption  a  relat1vely  large  oore  size  ts  required,  and  such
                                                   SICVCS WMS)   anti 7.Colitc anaings           matenals can  be  made  by  both  thermal  and  chemical  activation  procedures
                  Silica gel      Mkroporous silica                                              from  a  wide  range of carbonaceous starting materials. The activated carhons
                  Al-rich zeolites   Silica\ite,                                                 used  in gas adsorption generally have  much smaller pores, with a  substantial
                                   dealum1nated
                                   mordeoite, and                                                fraction  of the  total  ooros1tv  m  the  m1crooore  range.  These  adsorbents  are
                                   other silica-rich                                             generally made  by  thermal  activation from  a  relatively dense  form  of carbon
                                   zeolites                                                      such  as  bitummous  coal.  High·area  small~pore  carbons  mav  also  tie  made
                  Polymenc resins   Other polvmenc                                               from sources such as coconut shells, but the product generally has insufficient
                   comammg-OH      resins
                                                                                                 physical strength for PSA applicallons.
                    groups or cations

                                                                                                   •  A  useful  reference  1s:  C.  W.  Roberts,  "Moiecuiar Sieves  for  lndustrral  App!icaiions."  In
                   ~  For :i  deiailed discussmn of this topic:,  see: E.  F.  Vansan(.  Pore  Size  EnKmeerm,: m  Zeolites,   Properties and Applicatum.1· of Zeo/ites,  R.  P.  Townsend, ed., Sp·ecial  Puhl.  No.  33, The Chemical
                 Wiley  Chichester,  U.K.  (1990).                                               Society, London (198/IJ.
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