Page 43 - Pressure Swing Adsorption
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18                                    PRESSURE SWING ADSORPTION                  FUNDAMENTALS OF ADSORPTION                                    19
                 The  thermal  acl1vat1on  l)roccdurc  is  a  two-step  process  m  which  volatile
               matenal  1s  first  dnven  off  bv  controlled  pyrolysis  followed  by  a  controlled
               "burnout" of the pores using oxidizing gases such  as steam or CO at 800°C
                                                                      2
               (or  even  higher  temperatures).  7   The  surface  of  such  activated  carbons  is
               partially oxidized;  so  where  a  nonoolar surface  1s  required,  a  further  step  1s
               often  included,  10volving  either  evacuation  or  purging  with  an  mert  gas  at                                     •
               elevated temperature. This eliminates most of the oxides as  CO or CO •
                                                                          2
                 In  many  liquid-phase  applications  activated  carbon  is  used  m  powder                                  ~onqmol  i  J
               form,  but  for  gas-phase  applicatmns  larger particles  are  needed.  These  are                             () Jj 40Q•C  reqeneroted
               made  either directly  bv  crushing and screemng or more commonly by  granu-                              ·--- 0  0  ertiylbenzene  d
               lation  of the  powder  using  binders such  as  pitch, which  C<tn  he  act1valcd  to                          () Cl  ernyJbenu-ne  ..  uyre,.,e
                                                                                                                               $  ■ s1yrene   =j
               some extent during the  finai  thermai  treatment. The orcparation of activated
               carlxm  m  fiber  form  1s  a  relat1vely  new  development  which  holds  consider-                                         ~
               able nrom1se  for  the future. The diameter of the fibers  1s  small ( ~ 10 µm) so                          i                l
                                                                                                                 u  ,o·
               diffusional  resistance  is  reduced  to  an  mstgnificant  level.  To  date  such                .
               matenals do  not  appear  to  have  been  used  m  PSA  orocesscs,  but  the  raoid                            t•'---
               kinetics make this an intngumg possibility.                                                       0                  •-
                 The nreparauon of carbon moiecuiar sieves (Figure 2.3) ts  broadly similar                      '
               but  often  mcludes  an  additional  treatment  with  species  such  as  benzene  or              "
                                                                                                                                         •
                                                                                                                              'l'r■
                                                                                                                    10·' ,______________ •-:::::::_·
                                            Coal
                                             0                                                                        0      20      '0
                                            Grinding                                                              Corb-On  depos1t1on  ,  mg- coroon /  (J  •  MSC
                                                                                                 Figure 2.4  Effect of controlled carbon  deposition  on  sorptJon  rates  for  oxygen  and
                                                                                                                                                  5
                                                                                                 nitrogen  in  a carbon  molecular sieve.  (From  Chihara  and  Suzuki, with  oerm1ss1on.)
                                         OJ.idal!on  by  Ai,
                                            Ox1coal
                                                      Binder                                     actelvlene that are easily oolymenzed or cracked on  the  surface (Figure 2.4).
                                             0     D                                             By  careful  controi  of the  conditions  a  very uniform  pore  size  1s  achieved,  It
                                           Shapmg
                                                                                                 appears that  such control  1s  more  easily  achieved :by  carbon c1epos1tion  than
                                             0                                                   m  the  burnout  step.  Brief details  of some  representative  carbon  adsorbents
                                          Carbom:ullon                                           are included  in  Tahle 2.3.

                                       Urulo,m  Initial  Material
                                          D                                                        2.1. 7  Silica Gel
                              Sleam  Acl1Yallon       Treatment  under
                                                                                                 A  pure  silica  surface  1s  mactlve  and  "hyctroohobic,"  but  if  hydroxvl  groups
                              0                       Cracking  Conditions                       are present the surface becomes hydrophilic as  a result of the possibilities for
                              CMS  H2   Q             ol  Hydrocarbons                           hydrogen  bond  format10n.  Silica  "gel"  1s  formed  as  a  colloidal  precipitate
                                   Accrvaled  Carbon                                             when a  soluble silicate  ,s neutralized bv sulfunc acid. The size of the co!lidal
                                                         CMS  NZ                                 particles  and  the  nature  of  thetr  surface  are  strongly  mftuenced  bv  trace
                                                         CMS  02                                 components present rn  the solutJOn.  When water  is  removed  from  the  "gel,"
                Figure 2.3  Schematic diagram showmg the processes mvolved  in  the  manufacture of   an amorphous m1croporous solid  ts  formed,  but the size of the silica oartides
                carbon molecular sieve adsorbents. (From Junrgcn et ai.,1  with  perm1ss1on.)    and  therefore  the  pore  size  depend  on  ttle  conditions  dunng  ttle  water
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