Page 362 - Pressure Swing Adsorption
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 338   PRESSURE SWING ADSORPTION   APPENDIX  C                          339

 C.2.22  Kumar et al.   not perfectly understood.  In  addition,  1t  has  been: pos&ible  to secure  patents
           with  equivalent  ftowsheets  even  m  the  1980s  (cf  Figure  C.3).  Those  facts
 One -of  the  more  difficult  separations  among  atmospheric  gases  1s  to  split   speak volumes about the subtleties mvolved  m  PSA.
 argon  from  oxygen.  This is  due to nearly identical  adsorption  isotherms that   In one of the very first  disclosures of PSA concepts, Finlayson and Sharo  2
 these components exhibit with most zeolites.  Kumar et al., .who  filed  in  1982   made some suggest10ns that now  might  be  thought of as  mundane,  but were
 19
 and  received  a  patent in  1984,  approached  the problem of purifying argon   truly farsighted  at the time.  For example,  they  gave a  detailed  example of a
 containing nimor amounts (e.g .•  less  than 10% each) of nitrogen  and oxygen   smgle  PSA  system  bemg  used  to  alter  the  ratio  of  hydrogen  and  carhon
 by  first  removing the nitrogen vm  zeolite, then removing oxygen  usmg carbon   monoxide in  water gas from about  1 : 1 to 9: 1, 2: 1 and  J : 8,  respect1vciy,  for
 molecular sieve. Essentially,  they used  looseiy coupled  PSA systems m which   subseauent  synthesis  of ammonia,  methanol,  and  aliphatic  acids.  They also
 the  product  of  the  first  was  the  feed  to  the  second.  Followmg  similar   recognized  activated  carbon  and  silica  gel  as  promising adsorbents.  Finally,
 reasoning,  HayBshi  et  al.,  who  filed  in  1983  and  were  awarded  a  patent  in   they  suggested  that,  "nitrogen,  hydrogen,  oxyge·n,  carbon  monoxide,  and
 I 985,  211   were able  to split air to ob tam  both  high-purity oxygen  and argon.   methane"  were  candidates  for  purification  by  PSA.  Even  though  these
            applications were suggested over 60 years ago, the :PSA hydrogen purification
            (the  easiest  of the  group)  did  not  become  oractICal  on  a  commercial  scale
 C.2.23  Wiessner and Bolkart
            until  the  late  1960s.  Similarly,  separation· of either relatively pure oxygen  or
 A subtle variat1on,on the technique for recovering the most strongly adsorbed   mtrogen from  air  did  not  become  commercially  Viable  until  the  late  1970s,
 components from a mixture was suggested by Wiessner and Bolkart in  1988. 65   and splitting carbon monoxide  and methane from  contammants oniv hecame
 They allowed  blowctown  to an intermediate  pressure, then  purged  the  resid-  moderateiy successful  in  the late  1980s.  Despite the achievements of modern
 ual  heavy  component.  Subseauently,  they  completed  blowdown,  and  as  an   technology,  improvements  in  all  of  the  applications  are  still  bemg  sought.
 oot10n  purged agam. This allows  a valuable component to  be recovered at a   One wonders what,  if  Finiayson  and  Sharp were with  us  today,  they would
 a  moderately  adsorbed  component  to  be  removed  prior  to  dropping  the  l   In view  of the  incremental  nature of Batta's oa:tent  in  1971, 51   it could  be
 moderate  oressure, above  the mm1mum  pressure  m  the PSA cycle,  allowmg   expect to be possible via  PSA 60 years from  now.
 higher overall recovery with minimal recompression cost. It could also oermit
            though  of  as  a  sort  of turning  pmnt,  at  least  for  hydrogen  production.  It
 pressure sufficiently to desorb a  more strongly adsorbed comoonent.   !   seemed to mark the passage from  dramatic  mnovat1ons  m  which  substantial
   !
            improvements over  pnor art were  claimed,  to  an  onslaught of mmor  refine-
            ments  of existmg  cycles.  A  similar  turning  oomt :occurred ·for  PSA  oxygen
 C.2.24  Tagawa et al.
            production  in  the  eariy 1980s.  That  1s  not  to  say  that  mnovauons  ceased.  lt
 An  exampie  of the  refinement  that  1s  prevalent  m  recent  PSA  oatents was   was  Just  that  most  of the  "obvious"  modes  of  PSA  operatwn  had  aireadv
 given by Tagawa et al.  m  1988. 66   They compared three different methods for   been discovered, if ·not perfected.
 pr~ssure  eoualizatmn,  m  a  process to split oxygen from  air using SA zeolite.   Most of the topics covered in  this book are based on mathematicai models,
 Thelf opuons included; (1) from  the  product end of one column to the feed   although  in  some  instances  exoenmental  verification  is  mentioned.  Con-
 end  of a  parallel  column,  (2)  from  the  product  end  of one  column  to  the   versely,  this appendix:  covers the main  repository of ongmal id.eas  related  to
 oroduct end of a parallel column, and (3) from the feed end of one column to   pressure swing adsorption cycles, and apparently none of them depended on
 the feed end of a  parallel column. They state that the first  ts  m the onor art.   mathematical models  to reach fruition. This  is  not to say tl1at  some may  not
 They aiso claim that (2)  and (3) can be conducted simultaneously.   have  achieved  more  resounding  success  if an  adequate  mathematical  model
            had  been  available.  It  may  be  worthwhile  to  consider,  for  a  moment,  the
            remforcing  aspects  of  the  patent  literature  and  the  conclusions  obtamed
   I          For example,  there are  significant  distinct10ns  (n  the  ways  m  which  even
 C.3  Concluding Remarks   independently, though much  later, via  mathemat1c-a1  models.
 To close  this appendix, some comments are approoriate.  First,  a few  overall   l  i   the  simplest  steps  can  be  accomplished.  From  a  theoret1ca1  pomt  of view,
 1moress10ns are given about specific patents and phases that they seem to fall   i   Section 4.6 shows that pressunzation with product is v1rtually always suoenor
 into. Then  a few  comments are  made about  the  relation  of this appendix to   , I   to  pressurization  with  .feed.  That  potnt  1s  made  as  strongly,  if  not  as
 other parts of this book.   succinctly,  in  patents  by  different  methods  of  pressure  cquaiizi1t1on,  as
 First,  11  1s  remarkable  that  the  basic  ftowsheet  for  PSA  has  been  in  tile   !   illustrated  by  the  references  listed  m Sections C.2:8  and C.2.24.  Soecifieally,
    !       when  the purified  product from  one column 1s  use'd  partially to pressurize a
 public domam  for  over sixty years (cf.  Figure C.l), yet some  aspects are still
   l
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