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Kinetic study of hydrogen sulfide absorption in aqueous

chlorine solution

Jean-Baptiste Vilmain, Valerie Courousse, Pierre-Francois Biard, Mohamed

Azizi, Annabelle Couvert

To cite this version:

Jean-Baptiste Vilmain, Valerie Courousse, Pierre-Francois Biard, Mohamed Azizi, AnnabelleCouvert. Kinetic study of hydrogen sulfide absorption in aqueous chlorine solu-tion. Chemical Engineering Research and Design, Elsevier, 2014, 92 (2), pp.191-204..

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Submitted on 14 Nov 2013

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Kinetic study of hydrogen sulfide

absorption in aqueous chlorine solution

Jean-Baptiste VILMAINa,c

, Valrie COUROUSSEa,c

, Pierre-Franis BIAR!a,",c#

, M$a%e& A'I'Ia,c

,

Anna"elle COUVER(a,c

aEcle Natinale S)prie)re &e C$i%ie &e Rennes, CNRS, UMR *++*, Alle &e Bea)lie), CS ./01,

01./ Rennes Ce&e2 1, France

"Uni3ersit &e Rennes , CNRS, UMR *++*, 0 r)e &) Cls-C)rtel, BP 4.500, 01.5 Rennes Ce&e2 1,

France

cUni3ersit e)rpenne &e Breta6ne, ")le3ar& La7nnec, 0... Rennes, France

Graphical abstract

#Crrespn&in6 a)t$r8 Pierre-Franis BIAR! 9 (el8 :00 + +0 +0 / 1

E%ail-a&&ress8 pierre-;rancis


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Ab st ract

@&r6en s)l;i&e @+S is c)rrentl re%3e& ;r% 6ase)s e;;l)ents " c$e%ical scr)""in6 )sin6

Dater< C$lrine is a tp-6ra&e 2i&ant, reactin6 Dit$ @+S Dit$ a ;ast inetic rate an& en$ancin6 its

%ass trans;er rate< ( &esi6n, pti%ie an& scale-)p scr)""ers, nDle&6e ; t$e reactin inetics

an& %ec$anis% is re>)este&< ($is st)& in3esti6ates t$e @+S 2i&atin rate " reacti3e a"srptin in

a %ec$anicall a6itate& 6as-li>)i& reactr< Mass trans;er 6as an& li>)i& si&es %ass trans;er

ce;;icients an& $&r&na%ic inter;acial area per;r%ances ; t$e 6as-li>)i& reactr Dere

%eas)re& )sin6 apprpriate& p$sical r c$e%ical a"srptin %et$&s< ($e acc)rac ; t$ese

para%eters Das c$ece& " %&elin6 t$e @+S a"srptin in Dater Dit$)t 2i&ant< A sensiti3it

analsis cn;ir%e& t$e r")stness ; t$e %&el< Finall, reacti3e a"srptin ; @+S in c$lrine

sl)tin ;r aci&ic r circ)%ne)tral p@ allDe& t in3esti6ate t$e inetics ; reactin< ($e 3erall

2i&atin %ec$anis% c)l& "e &escri"e& ass)%in6 t$at @+S is 2i&ie& irre3ersi"l " "t$

$pc$lrite anin ClO- G *


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1

Introduction

@&r6en s)l;i&e @+S is a %ar t2ic c%p)n& in3l3e& in &r e%issins ; %an in&)stries s)c$

as Daste Dater treat%ent, p)lp in&)str, etc< ?stelD et al)e)s 2i&ant sl)tins at

"asic p@ are ;ten )se& Biar& et al)i& is )st &raine& D$en t$e salt acc)%)latin &)e t @+S 2i&atin int

s)l;ate anins "ec%es t $i6$)i& cntactr c$aracteriatin an& t$e inetic

cnstant &eter%inatin


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2

Mass transfer modeling

?as-li>)i& %ass trans;er can "e &escri"e& accr&in6 t 3ari)s t$eries< Us)all, t$e &)"le ;il%

t$er e2plicati3e sc$e%e in t$e s)pple%entar %aterial is applie& in stea& state $it%an,

4+0< ($e %lar ;l)2 trans;erre& ; an species A &J in %l %-+s- per s>)are %eter ; 6as-li>)i&

area can "e Dritten Perr an& ?reen, 4418

( ) ( )#& EqL A A L A AJ Ek C C K C C= = Eq. 5

E is t$e s-calle& en$ance%ent ;actr n )nit D$ic$ is t$e rati ; t$e a"srptin rate Dit$ an&

Dit$)t t$e reactin ;r an i&entical &i;;erence#

-A AC C < Ot$er &e;initins ; t$e en$ance%ent ;actr

can "e ;)n& in t$e literat)re< @De3er, t$is ne re%ains t$e %st enc)ntere&< CA,#,

Eq

A AC C are t$e

sl)te cncentratin respecti3el in t$e ")l %l %-0

, at t$e 6as-li>)i& inter;ace s)perscript # an&

in e>)ili"ri)% s)perscript E> Dit$ t$e 6as p$ase cncentratin G

AC &e&)ce& ;r% t$e @enrs laD8

G

Eq A A

A

A A

p R T CC

H H

= =

Eq. 6

pA is t$e partial press)re Pa, HA t$e @enrs laD cnstant Pa %0 %l

-< kL an& KL E>< 5 are

respecti3el t$e lcal an& 3erall li>)i& si&e %ass trans;er ce;;icients % s-

D$ic$ are line&

t6et$er t$r)6$ t$e ;llDin6 relatin8

L L A G

RT

K Ek H k = +

Eq. 7

kGis t$e lcal 6as si&e %ass trans;er ce;;icient< kLan& kGr&er ; %a6nit)&e are respecti3el .)i&-p$ase relati3e

%ass trans;er resistance RL, D$ic$ represents t$e rati ; t$e resistance lcate& in t$e li>)i& p$ase

&i3i&e& " t$e ttal resistance, is calc)late& " t$e ;llDin6 e>)atin @;;%ann et al


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)p Lee an& Pan6 (s)i, 444< At a %&erate i%peller spee&, t$e pDer inp)t is nt s);;icient t

&isperse t$e 6as in t$e part ; t$e reactr lcate& "elD t$e spar6er< In t$is case, t$e e2tent ; "ac-

%i2in6 is lD an& t$e ;lD can "e cnsi&ere& as a pl)6 ;lD< ($e rle ; t$e a6itatin is t "rea

")""les t %aintain a $i6$ inter;acial area< Ass)%in6 a pl)6 ;lD ;r t$e 6as an& a per;ectl %i2e&

li>)i&, t$e a"srptin rate Nin %l s-

can "e calc)late& " t$e ;llDin6 e>)atin8

( ) ( ) ( ), ,

,

,

ln

Eq Eq

A i A A o AEq

L A A L Eq

A i A

Eq

A o A

C C C C N K a V C C K a V

C C

C C

= =

Eq. 9

S)"scripts i an& re;er t t$e reactr inlet an& )tlet< a is t$e 6as-li>)i& inter;acial area %+%

-0

relati3e t t$e e;;ecti3e 3l)%e V< ($e %ass "alance ena"les t Drite8

( ), ,G G

G A i A oN Q C C =

Eq. 10

QGis t$e 6as 3l)%e ;lD rates %0s

-< Fr% E>s< *-.8

,

,

ln

G

A i

A

A

LG

A o A G A G

AL A GA

RTCC

H VRT a VRT K a

RTRTC H Q H QC

Ek H k H

= =

+

Eq. 11

$en t$e reactin rate is si6ni;icantl lar6er t$an t$e %ass trans;er rate, t$e sl)te is entirel

cns)%e& in t$e li>)i& ;il% an& CAten&s tDar& .< In t$e t$er cases, CA&epen&s n t$e li>)i& $l&-

)p, li>)i& resi&ence ti%e an& n t$e inetic an& %ass trans;er rates Lee an& Pan6 (s)i, 444< E2cept

;r tD li%it cases slD an& instantane)s reactins in t$e li>)i& ;il%, E&epen&s n t$e reactin

inetics< ($ere;re, its &eter%inatin in cntrlle& an& apprpriate& peratin6 cn&itins c)l&

ena"le inetics &eter%inatin< kLan& kGare %ainl in;l)ence& " t$e prperties an& $&r&na%ics

; respecti3el t$e li>)i& an& t$e 6as p$ases< ($e inter;acial area &epen&s n t$e 6as $l&-)p an&

")""les sie, D$ic$ are &eter%ine& " t$e ;lD ;iel&, t$e 6as ;lD-rate, t$e pDer inp)t an& t$e 6as

&ispersin c$aracteristic ; t$e i%peller RESI, +.0< E2cept t$e 6as si&e %ass trans;er ce;;icient

D$ic$ $as ne3er "een %eas)re& ;r a 6as-li>)i& a6itate& tan, t$e can "e esti%ate& )sin6 se%i-

e%pirical crrelatins Cal&er"an, 4/9 Cal&er"an, 449 Js$i et al


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3

Material and methods

!i;;erent c$e%ical sste%s Dere i%ple%ente& t &eter%ine a ne a"srptin in a sl)tin ;

$&r6en per2i&e, kLp$sical a"srptin ; p)re 26en, kGc$e%ical a"srptin ; @+S in $i6$l

cncentrate& c$lrine alaline sl)tin an& E @+S c$e%ical a"srptin in sli6$tl aci&ic r ne)tral

c$lrine sl)tin (a"le < @+S a"srptin in p)re Dater Das als in3esti6ate& t assess t$e acc)rac

; a, kLan& kG&eter%inatin< ($e para%eters are &e&)ce& ;r% t$e re%3al e;;icienc E>< + ;

eac$ a"sr"e& species8

=

, ,

,

G G

A i A o

A G

A i

C CEff

C Eq. 12

Table 1: Synthesis of the hysi!al an" !he#i!al oe$ating !on"itions alie".

Parameter ValueExperimental

uncertainty

Physical operating conditions

(e%perat)re T +40 H T H

E;;ecti3e 3l)%e V


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3#1

Presentation of the experimental set$up

($e la"ratr-scale 6lass 6as-li>)i& cntactr 1 in Fi6< is a n%inal + liters tan %ec$anicall

a6itate& " a R)s$tn t)r"ine i%peller &ia%eter ; 5)i& circ)latin6 in t$e reactr acet 5< ($e p@ ; t$e li>)i& an& t$e

te%perat)re are %eas)re& n-line )sin6 a c%"ine& p@-pr"e < Fres$ air is intr&)ce& )sin6 a 6as

p)%p !< ($en a 6as ;lD ; N+-@+S " is %i2e& Dit$ t$e p)%pe& air t$ans t a static %i2er 1#)i& cntactr is "-passe& t anale t$e 6as inlet at stea&-

state< Fr t$e inter;acial area &eter%inatin, t$e ;ee& sste% is replace& " an ne 6eneratr ;e&

Dit$ 26en< In t$is case, t$e ne ;lD rate is cntrlle& " a ;lD%eter in (e;ln< !)rin6 t$e

e2peri%ents, a ;ractin ; t$e 6as is "-passe& t anale t$e )tlet at stea&-state 12< Be;re

"ein6 release& in t$e at%sp$ere, resi&)al O0 an& @+S in t$e 6as p$ase Dere >)enc$e& )sin6

respecti3el an ne &estr)ctr an& " ")""lin6 in a cncentrate& "asic c$lrine sl)tin 13< ($e

6as press)re is %eas)re& tDice, at t$e ;lD%eter )tlet t crrect t$e ;lD rate an& in t$e reactr

$ea&space, )sin6 %an%eters)i& "ac %i2in6 per;ectl %i2e& li>)i& p$ase $as "een c$ece&

" Resi&ence (i%e !istri")tin R(! e2peri%ents ;r 3ari)s 6as . t /.. NL $-

an& li>)i& +. t

/. L $-

;lD rates an& i%peller spee& .. t /.. rp% )sin6 ;l)rescein as a tracer< It s$De& t$at

t$e li>)i& Das per;ectl %i2e& D$ile t$e i%peller spee& is lar6er t$an .. rp% D$ate3er t$e ;lD rate

in t$e ran6e i%ple%ente&< 05 Aci&-"aseA,+ D-pH :pH

.k

Kk

= =

E>< 0 Aci&-"aseA,+-pH+

+

.k

Kk

= =

E>< 0* Aci&-"aseA, A,+pH - pH0

0

.kKk

= =

E>< 01 @S-2i&atin

E>< 0/ @S-2i&atin

E>< 04 @+S 2i&atin

E>< 5. @+S 2i&atin


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($e en$ance%ent ;actr ;r tD irre3ersi"le parallel reactins in t$e li>)i& ;il% can "e &eter%ine&

)sin6 t$e On&a an& cDrers appr2i%ate& sl)tin ;r t$e tD-;il% t$er Biar& et als< 5+ an& 50 are tD in&epen&ent e>)atins Dit$ 0 3aria"les /, an& E< ($ere;re, an a&&itinal

e>)atin is re>)ire&< On&a et al< 41. ass)%e& t$at t$e rea6ent cncentratins are >)a&ratic

;)nctins ; t$e ;il% t$icness an& "taine& t$e ;llDin6 e>)atin8

( )

=

+

*

1

*

1

*

*

C%+H

C%+

C%+H

C%+

k/

k

k /

k /

Eq. 45

FllDin6 t$e n)%erical prce&)re &e3elpe& in t$e s)pple%entar %aterial, **


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crr"rates t$e ass)%ptin t$at @+S can react Dit$ ClO- t$r)6$ an aci& "ase reactin "e;re

2i&atin< ( assess t$e i%prtance ; "t$ reactins Dit$ ClO-an& ClO@, t$e rati E04[E04:5. ; t$e

en$ance%ent ;actr calc)late& ass)%in6 )st t$e reactin Dit$ ClO- n t$e 3erall en$ance%ent

;actr $as "een calc)late& (a"le 5< It cn;ir%s t$at, e2cept ;r circ)%ne)tral an& "asic p@, "t$

reactins cntri")te t t$e 3erall %ass trans;er en$ance%ent)ire& t sl3e t$e $i6$ n)%"ers ; &i;;erential e>)atins an& ;inall ")il& a %&el

D$ic$ can pr3i&e an e;;icient tl ;r scr)""ers &esi6n


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,

Conclusions

Hinetics ; @+S reactin Dit$ $pc$lrite anin an& $pc$lr)s aci& Das in3esti6ate& " reacti3e

a"srptin in a Dell a6itate& 6as-li>)i& cntactr< ($e li>)i& an& 6as si&es %ass trans;er ce;;icients

as Dell as t$e inter;acial area $as "een &eter%ine& )sin6 apprpriate& e2peri%ental cn&itins

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