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Removal of Chromium by Ion Exchange

10/25/2013 Ben Green Roxana Lopez

Removal of Chromium by Ion Ex han!e

"any impuri#ie$ an% #oxi $ub$#an e$ preven# &a#er from bein! u$eable' (hi$ i$ orre #e% &i#h #he #rea#men# of &a#er by removin! #he$e impuri#ie$ an% o#her un&an#e% $ub$#an e$' (here are many #oxi me#al$ #ha# an on#amina#e &a#er' I# i$ impor#an# #o on$i%er #he role of Chromium in &a#er$ %ue #o #hi$ rea$on' )i!h level$ an be #oxi #o human$ an% #he environmen#' Introduction Background Chromium an exi$# in $everal hemi al form$ &i#h oxi%a#ion number be#&een 0 an% *' +,o#a$ an% -#a$i .a/ 20000' (here are #&o %ominan# form$ of Chromium1 #rivalen# +Chromium III0 an% hexavalen# +Chromium 2I0+3- E45/ 20000' 6i#h #he ex#ra #e% hromium/ i# an be u$e% #o ma.e me#al$ an% alloy$ +3- E45/ 20000' (he #rivalen# ion i$ u$eful in human$ for #heir %ie#/ bu# #he hexavalen# ion an be harmful +3- E45/ 20000' Chromium III i$ le$$ #oxi #han Chromium 2I +Bazzi e# al'/ 20050' (herefore/ #he amoun# allo&e% in %rin.in! &a#er mu$# be moni#ore% &i#h $#rin!en# re!ula#ion$ in or%er #o re%u e #he a%ver$e effe #$' Chromium i$ a$$o ia#e% &i#h bo#h benefi#$ an% ne!a#ive$ &i#hin heal#h an% $o ie#y' )exavalen# hromium i$ la$$ifie% a$ an oxi%izin! a!en# +3- E45/ 20100' Be au$e hromium help$ #he human bo%y onver# !lu o$e #o ener!y/ i#$ me%i al u$e$ vary &i%ely +3- E45/ 20000' ,ey u$e$ of hromium in lu%e heal#h are an% me%i ine$' Cer#ain amoun#$ of Chromium are even ne e$$ary for #he human bo%y #o perform ri!h#' -ome pharma eu#i al purpo$e$ in lu%e bloo% $u!ar level$ for people &i#h er#ain #ype$ of

%iabe#e$' 5l$o $ome o#her me%i al u$e$ in lu%e %epre$$ion/ hear# me%i a#ion/ an% &ei!h# lo$$' Chromium al$o %i$play$ many u$eful purpo$e$ &i#h #he in%u$#rial an% manufa #urin! $e #or$' Chromium i$ u$e% #o har%en $#eel/ u$eful for #ool$ an% $#eel manufa #urin! e7uipmen# #ha# %eal$ &i#h ex#reme hea#$ an% o#her har% me#al$' Chromium i$ a .ey in!re%ien# #o rea#in! $#ainle$$ $#eel +,rop$ ho# an% 8oebri h/ 20100' -#ainle$$ $#eel &i#h i#$ non9ru$#in! 7uali#y i$ %e$ire% in many re$i%en#ial an% ommer ial proper#ie$ for i#$ ex#ernal hara #eri$#i $' Chromium i$ al$o involve% in #he rea#ion of many o#her alloy$' Chromium i$ al$o a%%e% #o er#ain #ype$ of !la$$ #o rea#e a olor effe #'

Chromium Contamination Chromium in &a#er a# #oo hi!h of on en#ra#ion$ oul% a%ver$ely affe # #he &a#er:$ u$er$' 6a#er na#urally arrie$ only #ra e$ amoun# of hromium/ ho&ever #he variou$ in%u$#rie$ u$in! #he elemen# have in rea$e% #he hromium on#en# &i#hin &a#er' "e#al $urfa e refinerie$ or in%u$#rie$ rea#in! lea#her all on#ribu#e hromium #o #he af#er $our e +3- E45/ 20100' (oo mu h on en#ra#ion of hexavalen# hromium ha$ le% #o environmen#al i$$ue$ an% #hi$ i$ #he rea$on for #rea#men# of #he hromium' Chromium i$ an i%en#ifie% ar ino!en' Chromium an au$e lun! an er in hi!h enou!h on en#ra#ion$ +3- E45/ 20100' Chromium an al$o au$e aller!i %erma#i#i$ &hen expo$e% for lon!er perio%$ of #ime +3- E45/ 20000' (here are po$$ibly o#her heal#h effe #$ #ha# hromium mi!h# have' Chromium * in par#i ular an au$e perfora#ion of #he na$al $ep#um/ a$#hma/ bron hi#i$/ an% inflamma#ion of #he larynx an% liver +,o#a$ an%

-#a$i .a/ 20000' Chromium an even be le#hal in on en#ra#ion$ of 0'1m!/! of bo%y &ei!h# +Ri har% an% Bour!/ 1;;10' (he E45 an% o#her environmen#al a!en ie$ are in har!e of fi!urin! ou# any hazar% #ha# impuri#ie$ in &a#er may have a$ &ell a$ $e##in! maximum level$ of on en#ra#ion for #he$e' Chromium an be u$e% for ma.in! $#eel an% alloy$ an% for lea#her pre$erva#ion/ ele #ropla#in!/ an% #ex#ile in%u$#ry/ amon! o#her u$e$ +3- E45/ 20100' Chromium an #herefore be foun% in in%u$#rial &a$#e&a#er$ &i#h on en#ra#ion$ be#&een 0'5 < 10 mi ro!ram$ per li#er +Barboo#i/ 20100' I# an al$o be na#urally foun% in #he ear#h=$ !roun%&a#er &i#h a #ypi al on en#ra#ion le$$ #han 5 mi ro!ram$ per li#er +6orl% )eal#h >r!aniza#ion/ 20030' (hi$ varie$ %epen%in! on #he re!ion bein! analyze% an% &he#her i#=$ !roun%&a#er or $ea&a#er' Curren#ly/ #he maximum on#amina#ion level +"CL0 i$ 100 ppb +3- E450' Le!i$la#ion re7uire$ #ha# #he on en#ra#ion of hromium be le$$ #han 0'5 m!/L re!ar%le$$ of oxi%a#ion $#a#e +>nyan ha e# al'/ 200?0'

(Reyes-Gutierrez, 2009)

(he $pe ie$ per en# v$ #he p) i$ $ho&n above' 5# a p) of */ #here i$ a fra #ion of ea h $pe ie$ of Chromium 2I' 5$ #he p) in rea$e$/ #he $pe ie$ of #he Chromium #ha# i$ %ominan# han!e$' 6hen #he p) i$ !rea#er #han *'@/ Cr>A i$ #he %ominan# $pe ie$/ an% i$ almo$# #he only $pe ie$ pre$en# a# a p) of ?'5 an% !rea#er'

Ion-exchange 6a#er on#ain$ ion$ in lu%in! hromium ion$/ &hi h i$ #he fo u$ of #hi$ labora#ory' (here are variou$ pro e$$e$ #ha# an remove hromium ion$ in lu%in!/ re%u #ion an% pre ipi#a#ion/ ion ex han!e/ an% a%$orp#ion +Ren!araB e# al/ 20010' Ion ex han!e u$e$ re$in$' -al#$ u$e a fixe% number of anion$ an% a#ion$ in i#$ hemi al ompo$i#ion' Common #able $al#/ for example/ ha$ a one #o one propor#ion of $o%ium #o hlori%e ion$ +Rohm an% )aa$/ 200?0' Ion ex han!e re$in$ are very $mall/ abou# 0'* mm in %iame#er +Rohm an% )aa$/ 200?0' Ion ex han!e remove$ er#ain ion$/ %epen%in! on &he#her re$in a##ra #$ anion$ or a#ion$' -ome ion9ex han!er$ even have preferen e$ for er#ain ion$ over o#her$ %epen%in! on i#$ hemi al ompo$i#ion' Ion ex han!e remove$ hromium ion$ by repla in! i#$ anion &i#h an anion from #he re$in %e$i!ne% for #hi$ purpo$e +Rohm an% )aa$/ 200?0' 5$ &a#er pa$$e$/ #he hromium ion$ are ex han!e% in #he re$in for hlori%e$ or hy%roxi%e$ or o#her ion$ %epen%in! on #he #ype of re$in u$e%' -ome a%van#a!e$ of ion ex han!e are #ha# ha$ re overy of me#al value/ $ele #ivi#y/ an% le$$ $lu%!e volume +Ren!araB e# al'/ 20010' Re$in$ oul% al$o be re!enera#e% #hrou!h a pro e$$ alle% re!enera#ion' 6a$hin! #he olumn #o remove #he $u$pen%e% $oli%$ %oe$ #hi$' (he re!eneran# $olu#ion i$ #hen pla e% in re$in +Rohm an% )aa$/ 200?0' Ion$ are #hen a##a he% #o #hi$' (hi$ i$ #hen

rin$e% ou# an% #he re$in i$ re!enera#e%' Ea h re$in ha$ $ome#hin! alle% a $ele #ivi#y oeffi ien#' -ele #ivi#y oeffi ien#$ are a mea$ure of #he pre%ile #ion of er#ain re$in$ for er#ain ion$' (he$e oeffi ien#$ are %epen%en# upon #he ra%iu$ &hen hy%ra#e% an% #he ioni har!e of #he ion$' (he oeffi ien# i$ al$o %epen%en# on #empera#ure/ pre$$ure/ an%

ompo$i#ion of bo#h pha$e$ +"arina e# al/ 1;;10' -ele #ivi#y oeffi ien#$ apply only over a $mall ran!e of on en#ra#ion$' (here are #&o %ifferen# #ype$ of re$in overall #ha# an be u$e%' (hey are $ele #ive re$in$ an% non$ele #ive re$in$' Con$ele #ive re$in$ ab$orb many ion$ an% have a !rea#er preferen e for ion$ &i#h many har!e$ an% a# hi!her on en#ra#ion$ #han o#her ion$ +8>6ED0' -ele #ive re$in$ are %e$i!ne% #o have a preferen e for a er#ain #ype of ion ba$e% on i#$ hemi al ompo$i#ion +8>6ED0' (he %ifferen e be#&een $ele #ive an% non$ele #ive i$ #ha# $ele #ive prefer$ a er#ain #ype of ion %e$pi#e #he on en#ra#ion$ of o#her ion$ #ha# may have #he $ame har!e' (hi$ an be u$eful be au$e &hen #here are a hi!h number of o#her impuri#ie$ #ha# aren=# e$$en#ial #o remove' (here are al$o ion$ #ha# nee% #o be remove% #ha# are in a $maller on en#ra#ion1 #he $ele #ive re$in an be u$e% #o ma.e $ure #ha# #he ion$ are remove% &i#h no problem'

a! "x#$anation (hi$ lab %eal$ &i#h #he ion ex han!e for #he removal of Chromium' 6ha# #hi$ mean$ i$ a re$in &ill be a%%e% #o a Chromium $ample' (he purpo$e of #hi$ re$in i$ #o #a.e #he ion$ from #he hromium a&ay an% allo& lean &a#er #o pa$$' (hi$ neu#ralize$ #he $ample &hile har!in! #he re$in$' >n e #he re$in rea he$ i#$ apa i#y/ #he re$in mu$# be re!enera#e%' (hi$ i$ u$ually %one u$in! a re!enera#in! olumn' In #hi$/ #he ex han!e%

ion$ are rein#ro%u e% #o #he re$in #hrou!h a hi!hly on en#ra#e% brine &i#h a $#ron! a##ra #ion for #he$e ex#ra ion$ a$ &ell' (he ion$ are #hen #a.en from #he re$in #o #hi$ ne& $ub$#an e/ u$ually a #ype of $al#/ an% #he re$in$ are re har!e% an% rea%y #o ion ex han!e &i#h a on#amina#e% &a#er a!ain' If re!enera#ion &a$ no# applie%/ #he re$in$ &oul% no# be a$ effe #ive an% may even even#ually no# &or. a# all' 6i#h all #he heal#h effe #$ of Chromium on#amina#ion/ an% a $#ri # "CL $e# by #he E45/ Chromium i$ a bi! priori#y #o remove from %rin.in! &a#er' I!norin! #he hromium a%ver$e effe #$ oul% lea% #o an environmen#al %i$a$#er Bu$# a$ ea$y &hi h i$ &hy i# i$ impera#ive for #he $#u%y an% #rea#men# of #hi$ elemen#' Chromium III an be benefi ial #o a per$on:$ heal#h' )o&ever/ #he hexavalen# ion of Chromium i$ %e#rimen#al'

Experimental Procedure Batch %est Eor #hi$ par# of #he experimen#/ $ix bo##le$ apable of hol%in! 100 mL of $ample &ere u$e%' (he $#ar#in! on en#ra#ion of hromium in &a#er for #hi$ experimen# &a$ 200 F!/L/ or 0'2 m!/L' -#o . $olu#ion of Chromium u$e% &a$ 1000 F!/L' (o ob#ain #he %e$ire% $#ar#in! on en#ra#ion/ 20 mL of hromium &a$ a%%e% in#o ea h bo##le' (hi$ value &a$ on$i$#en# for ea h bo##le in or%er #o %e#ermine #he effe #ivene$$ of #he re$in on hromium %epen%en# on varyin! amoun#$ of $ulfa#e' -ulfa#e &a$ varie% in #hi$ por#ion #o %e#ermine #he effe # i# ha% on #he removal of hroma#e ba$e% on #he re$in u$e%' Con en#ra#ion$ of $ulfa#e &ere 5/ 10/ 25/ an% 50 m!/L' -in e #he $#o . $olu#ion of $ulfa#e u$e% &a$ 500 m!/L/ #he amoun# a%%e% #o #heir re$pe #ive bo##le$ &ere 1/ 2/ 5/ an% 10 mL' Ba$e% on #he apa i#y of #he 5-B92 re$in/ #he amoun# of re$in a%%e% #o ea h bo##le &a$

al ula#e% #o be 0'02 !' (he remain%er of ea h bo##le &a$ fille% u$in! %eionize% +8I0 &a#er' (hi$ informa#ion i$ #abula#e% belo&' Bottle Number Control 1 2 80 79 78

Blank DI Water (mL) S 4!2 (mL) Cr (mL) "e#$n (%) 79

3 75 5 20 0&02

4 70 10 20 0&02

1 0 1 2 20 20 20 20 0 0&02 0&02 0&02 Table 1 Volume of Li uid! added

5f#er a%%in! #he 8I &a#er/ $ulfa#e/ hromium/ an% re$in/ #he Gblan.H bo##le &a$ mea$ure% #o fin% #he preliminary on en#ra#ion$ ba$e% on #he volume$ a%%e%' Chromium &a$ mea$ure% by a%%in! 10 mL of $ample in#o a vial &i#h a hromium9rea #an# rea!en# pillo&' 5f#er allo&in! ? minu#e$ for #he olor #o fully %evelop/ #he vial &a$ pla e% in#o #he $pe #ropho#ome#er u$in! #he pre$e# hromium pro!ram #o ob#ain #he on en#ra#ion' (he pro!ram &a$ able #o rea% a on en#ra#ion be#&een #he ran!e$ of 090'@00 m!/L' -ulfa#e &a$ al$o mea$ure% by pla in! 10 mL of $ample in#o a vial &i#h a $ulfa#e9rea #an# rea!en# pillo&' 5f#er allo&in! 20 minu#e$ for #he olor #o fully %evelop/ #he vial &a$ pla e% in#o #he $pe #ropho#ome#er u$in! #he pre$e# $ulfa#e pro!ram #o ob#ain #he on en#ra#ion' (he pro!ram &a$ able #o rea% a on en#ra#ion be#&een #he ran!e$ of 09@0 m!/L' (he remain%er of #he bo##le$ &ere pla e% in#o a $ha.er an% $ha.en for 2A hour$' 5f#er #he allo##e% #ime/ #he on en#ra#ion$ of hromium an% $ulfa#e &ere mea$ure% u$in! #he $ame me#ho% a$ before' In #he #e$#in! of Bo##le A/ #he $ulfa#e on en#ra#ion &a$ %ilu#e% u$in! 5 mL of $ample an% 5 mL of 8I &a#er $o a$ no# #o ex ee% #he ran!e'

Co$umn %est

5 3 L ba# h of $#o . $olu#ion &a$ rea#e% on#ainin! 0'AA? m!/L of Chromium an% 200 m!/L of -ulfa#e' 5 1 m %iame#er olumn &a$ u$e% for #he #e$#' 20 mL of pre9 &e##e% re$in &a$ a%%e% #o #he olumn' 5 $mall #ube &a$ in$er#e% in#o #he 3 L $ample of $olu#ion/ an% ano#her #ube in$er#e% in#o #he olumn' 3$in! a pump/ #he &a#er &a$ #ran$ferre% from #he $olu#ion #o #he olumn' (he &a#er &a$ #hen expo$e% #o #he re$in an% allo&e% #o %rip #hrou!h an% exi# #he olumn' I# &a$ impor#an# #o e7ualize #he flo& ou# &i#h #he flo& in $o a$ #o no# overflo& or un%erflo& #he olumn/ bu# ra#her have on#inuou$ flo&$ #hrou!hou#' (he exi#in! &a#er &a$ allo&e% #o fill a !ra%ua#e% ylin%er' 100 mL $ample$ of &a#er &ere #a.en af#er &a$#in! 300 mL' (he $amplin! pro e$$ &a$ repea#e% for #he re$# of #he experimen#' (he $ample$ #a.en &ere #e$#e% a or%in! #o #he )5C) #e$#in! pro e%ure$ for Chromium an% -ulfa#e' (he$e are #he $ame pro e%ure$ a$ men#ione% in #he ba# h #e$#in! por#ion' >n e #he re$in ha% been exhau$#e%/ i# &a$ ne e$$ary #o re!enera#e #he re$in in or%er #o ma.e i# u$eable on e a!ain' (o %o #hi$/ hi!hly on en#ra#e% brine &a$ u$e%' (he brine &a$ run #hrou!h #he olumn in #he $ame manner a$ #he experimen#al por#ion above/ bu# #he $ulfa#e an% hromium &a$ bein! remove% from #he re$in'

Re!ult! and "i!cu!!ion Batch %est (he re$ul#$ from #he ba# h #e$# are #abula#e% belo&' ->A +m!/L0 Cr +m!/L0
92

Blan. 3? 0'2A

Con#rol 1 2 0 3 3; 0'0A 0'0A 0'0@ Table # Ending Concentration!

3 *3 0'0?

A *5 0'11

5$ #he #able above $ho&$/ #he re$in &a$ effe #ive a# removin! bo#h #he -ulfa#e an% Chromium from #he &a#er' (he blan. on#aine% 1 mL of -ulfa#e an% 20 mL of Chromium' Co re$in &a$ a%%e% in or%er #o have a ba$e on en#ra#ion' In #he on#rol/ only re$in an% Chromium &ere a%%e%' (hi$ reveale% ho& #he re$in remove% #he Chromium &i#hou# -ulfa#e hin%erin! i#' (he o#her four bo##le$ in #he ba# h #e$# ha% varyin! amoun#$ of -ulfa#e a%%e% #o #hem/ ran!in! from 1 mL #o 10 mL' 5$ #he re$ul#$ #able $ho&$/ $ulfa#e %oe$ have an effe # on ho& #he re$in remove$ #he on#aminan#' 5$ more -ulfa#e i$ a%%e%/ le$$ Chromium i$ remove% from #he &a#er' In bo##le A/ no# enou!h Chromium &a$ remove% #o mee# #he "CL of 0'1 m!/L' >#her&i$e/ Chromium &a$ effe #ively remove% %e$pi#e #he pre$en e of -ulfa#e in #he &a#er'

Co$umn %est 8urin! #he olumn #e$#/ #he re$in effe #ively remove% mo$# of #he hromium an% $ulfa#e' (he re$in &a$ $o effe #ive/ in fa # #ha# #he brea.#hrou!h &a$ never a #ually rea he%' 5l#hou!h #he olumn &a$ run in ex e$$ of #he al ula#e% #ime of 3'?2 hour$/ an% in ex e$$ of #he al ula#e% volume of 3 L/ #he apa i#y &a$ never rea he%' (hi$ may be a al ula#ion error/ ho&ever #he $ame error$ oul% be foun% &hen ompare% #o variou$ !roup$ runnin! #he experimen#' (he $pe $ on #he re$in oul% have been on$erva#ive value$ $o a$ no# #o overloa% #he re$in' 5 !raph of #he umula#ive volume run #hrou!h #he olumn v$' #he effluen# on en#ra#ion$ i$ $ho&n belo&'

&igure '- Cumu$ati(e %hrough#ut )o$ume (s* "++$uent Concentration

5$ #he fi!ure $ho&$/ #he on en#ra#ion of Chromium %i% no# vary !rea#ly %e$pi#e #he amoun# of $olu#ion run #hrou!h #he olumn' (he experimen# &a$ #ermina#e% af#er 5*00 mL of $olu#ion &a$ u$e%' Ba$e% on #he re$ul#$/ i# an be inferre% #ha# #he apa i#y of #he re$in &a$ no# ex ee%e%/ an% #herefore a brea.#hrou!h urve oul% no# be rea#e%' In #heory/ #he brea.#hrou!h poin# $houl% have been rea he% !iven #he ini#ial 3 L of $olu#ion' (hrou!hou# #he %ura#ion of #he experimen#/ $ulfa#e &a$ omple#ely remove%' (he volume of re$in u$e% oul% han%le even more $olu#ion/ an% $#ill be effi ien# a# removin! #he on#aminan#$' 5$ $ho&n in Ei!ure 1/ #he on en#ra#ion of #he effluen# &a#er ran!e% from 0'01 m!/L #o 0'05 m!/L' 5ll of #he$e value$ are un%er #he ran!e of "CL for %rin.in! &a#er of 0'1 m!/L' (herefore/ #he re$in ex elle% a# removin! bo#h #he -ulfa#e an% Chromium from #he &a#er' Conclu!ion!

(he re$in u$e% &a$ very effe #ive in removin! #he on#aminan#$ from #he &a#er' In #he ba# h #e$#/ #he $ame amoun# of re$in remove% on#aminan#$ &i#h varyin! on en#ra#ion$' 6hen no -ulfa#e &a$ a%%e%/ #he Chromium &a$ re%u e% #o 0'0A m!/L/ &ell &i#hin #he "CL' 6i#h #he a%%i#ion of $ulfa#e/ #he Chromium &a$ re%u e% belo& #he "CL in all bu# one in$#an e' -ulfa#e &a$ al$o effe #ively remove% in mo$# of #he ba# he$' 5l#hou!h -ulfa#e %oe$ have an effe # on #he re$in=$ effi ien y #o remove Chromium/ #he more $#rin!en# on#aminan# &a$ $#ill remove% #o &i#hin a ep#able level$' (he be!innin! on en#ra#ion$ from #he $olu#ion #ha# &a$ ma%e for #he olumn #e$# &ere re%u e% #o a value &ell belo& #he "CL $e# by #he E45' In pra #i e/ #he re$in u$e% &oul% be a !oo% re$in #o u$e for #he removal of Chromium' In fa #/ i# an be inferre% #ha# &a#er &i#h a hi!her on en#ra#ion of Chromium/ or more &a#er &i#h #he $ame on en#ra#ion$ oul% have been u$e%' (he experimen# %emon$#ra#e% #he effe #ivene$$ of Ion9ex han!e in #he removal of on#aminan#$ in &a#er' (hi$ pro e%ure oul% be u$e% &i#h o#her on#aminan#$ a$ &ell/ $o i# i$ a benefi ial #e hnolo!y for ma.in! %rin.in! &a#er #ha# i$ &i#hin #he a ep#able limi#$ $e# by #he E45'

References

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