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Journal of PetroleumScience and Technology
*Corresponding author
Asghar Molaei Dehkordi
Email: [email protected]
Tel: +98 21 6616 5412
a!:+98 21 66"2 285#
Article history
$e%ei&ed: 'u(e 25) 2"1#
$e%ei&ed i( re&ised form: *e,em-er 14) 2"1#
A%%e,ed: 'a(uar "6) 2"14
A&aila-le o(li(e: Mar%h 1") 2"14
Journal of Petroleum Science and Technology 2014 , 4/10) 29#8 h,,:3s,.rii.ir
2"14 $esear%h (s,i,u,e of e,roleum (dus,r /$0
29
BIODESULFURIZATION OF SIMULATED LIGHT FUEL OIL BY A
NATIVE ISOLATED BACTERIA BACILLUS CEREUS HN
aryush Ara!ian" #elya $a%afi" &atola &arhadi" and Asghar 'olaei eh(ordi*
Dear,me(, of 7hemi%al a(d e,roleum E(gi(eeri(g) *harif (i&ersi, of Te%h(olog) .. o! 111559465)
Tehra() ra(
ABSTRACT
( ,he rese(, aer) ,he -iodesulfuri;a,io( of simula,ed ligh, fuel oil /i.e.) di-e(;o,hiohe(e /DT0
i( dode%a(e0 a(d u(,rea,ed kerose(e <i,h a high ,o,al sulfur %o(,e(, has -ee( s,udied - a (a,i&e
isola,ed -a%,erium (amed Bacillus cereus =>. The i(flue(%es of &arious arame,ers su%h as ,he
rea%,io( ,emera,ure /T 0) -io%a,als, %ell de(si,) oil hase fra%,io( /0) a(d i(i,ial DT
%o(%e(,ra,io( o( ,he fra%,io(al %o(&ersio( of ,he model sulfur %omou(d <ere i(&es,iga,ed. The
e!erime(,al da,a o-,ai(ed <ere used ,o de,ermi(e ,he rea%,io( ra,e %o(s,a(, of ,he model sulfur
%omou(d a(d ,he %orreso(di(g a%,i&a,io( e(erg. ur,hermore) ,he -iodesulfuri;a,io( of u(
,rea,ed kerose(e <i,h a ,o,al sulfur %o(,e(, of 2### m< rodu%ed - a( ra(ia( refi(er
%oma( /sfaha( refi(er0 <as i(&es,iga,ed ,o e!ami(e ,he %aa-ili, of ,his (e< mi%roorga(ism.
, <as reali;ed ,ha, a-ou, ##? of ,he ,o,al sulfur %o(,e(, of u(,rea,ed kerose(e %ould -e remo&ed
af,er 2 hrs. The resul,s of ,he reso(se surfa%e me,hodolog /$*M0 sho<ed ,ha, a uadra,i%
%orrela,io( %ould -e roosed for ,he i(flue(%es of -io%a,als, %ell de(si,) ) a(d i(i,ial DT
%o(%e(,ra,io( o( ,he desulfuri;a,io( of DT.
)eyords: iodesulfuri;a,io() DT) $*M) Bacillus cereus =>) *imula,ed Bigh, uel il
INTRODUCTION
The %om-us,io( of fossil fuels releases a huge
amou(, of *! i(,o ,he a,moshere) <hi%h has
ad&erse effe%,s o( ,he e(&iro(me(,. e%ause of
,he ,ra(sor,a,io( of *! - air s,reams) i(,er(a
,io(al %ooera,io( is reuired ,o %o(,rol emis
sio(s C1) 2. To ha&e a less ollu,ed <orld) a
(um-er of regula,io(s ha&e -ee( e(a%,ed ,o
res,ri%, ,he sulfur %o(,e(, of fossil fuel oils)
rimaril ,hose i(,e(ded for ,ra(sor,a,io( C#. (
,he as, de%ades) ,he allo<ed ,o,al sulfur %o(,e(,
of ,ra(sor,a,io( fuel oils has -ee( redu%ed from
2"""5""" m ,o less ,ha( 15 m C4.
The sulfur%o(,ai(i(g %omou(ds of %rude oil
ha&e ma( differe(, s,ru%,ures su%h as eleme(,al
sulfur) hdroge( sulfide) sulfides) mer%a,a(s)
a(d he,ero%%les. Amo(g ,hese grous) he,ero
%%les su%h as di-e(;o,hiohe(e /DT0 or i,s
deri&a,i&es are ui,e imor,a(,) -e%ause ,he
ha&e higher -oili(g oi(,s /larger ,ha( 2"" 70)
<hi%h makes i, is diffi%ul, ,o remo&e ,hem from
,he a,mosheri% ,o<er ou,le, s,reams of oil refi(
eries C5) 6. ( addi,io() u ,o "? of sulfur i(
hea& fuel oils is i( ,he form of di-e(;o,hiohe(e
/DT0 a(d i,s alkla,ed deri&a,i&es C. The
%o(&e(,io(al me,hod for remo&i(g sulfur
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Journal of Petroleum
Science and Technology D. Ara-ia() =. >a3afi) . arhadi) a(d A. Molaei Dehkordi
Journal of Petroleum Science and Technology 2014) 4/10) 29#8 h,,:3s,.rii.ir
2"14 $esear%h (s,i,u,e of e,roleum (dus,r /$0
+0 ,
%o(,ai(i(g %omou(ds of ligh, fuel oils is
hdrodesulfuri;a,io( /=D*0) <hi%h has oor
erforma(%e i( remo&i(g some he,ero%%li% %om
ou(ds su%h as ,hiohe(es) -e(;o,hiohe(es)
di-e(;o,hiohe(e) a(d ,heir deri&a,i&es - usi(g%o(&e(,io(al %a,als,s. =o<e&er) (e< de&eloed
%a,als,s %a( o&er%ome ,he oor erforma(%e of
=D*.
iologi%al desulfuri;a,io( /D*0) <hi%h a,,ra%,ed
resear%h effor,s i( ,he oil i(dus,ries C8) 9) is a
ro%ess for ,he desulfuri;a,io( of fossil fuel oils
- mea(s of e(;me%a,al;ed rea%,io(s C1". (
,his ro%ess) a -io%a,als, i( a( aueous solu,io(
is %o(,a%,ed <i,h a fuel oil /orga(i% hase0 ,o -e
,rea,ed a(d ,he desulfuri;a,io( rea%,io(s o%%ur
a, ,he i(,erfa%e of ,he aueous a(d orga(i%
hases. DT a(d i,s deri&a,i&es <ere <idel
used for ,he desulfuri;a,io( of simula,ed ligh,
fuel oils. The se%ifi% o!ida,i&e desulfuri;a,io( of
DT is a a,h<a i( <hi%h %ar-o(sulfur -o(d is
,arge,ed ,o rodu%e 2hdro!-ihe(l as ,he
fi(al rodu%, C11. D* is (ormall %arried ou, a,
mild oera,i(g ,emera,ure a(d a,mosheri%
ressure a(d -io%a,als, ro&ides a highl sele%,i&e desulfuri;a,io(. Moreo&er) i( ,his ro%ess)
gree(house emissio(s) %ai,al) a(d oera,i(g
%os,s are lo<er ,ha( ,hose of =D* C12.
7o(sideri(g ,hese ad&a(,ages) a (um-er of
s,udies o( ,his ro%ess regardi(g &arious ,es
of effi%ie(, mi%roorga(isms ha&e -ee( reor,ed
C1#F16. ( addi,io() (umerous i(&es,iga,ors
ha&e s,udied ,he i(flue(%es of -io%a,als, %ell
de(si,) oil hase fra%,io() a(d i(i,ial DT
%o(%e(,ra,io( as ,he mos, imor,a(, arame
,ers of D* ro%ess o( ,he desulfuri;a,io( of
ligh, fuel oils C1F19.
The ma3or o-3e%,i&e of ,he rese(, <ork <as ,o
i(&es,iga,e ,he imor,a(, arame,ers of D* -
a (a,i&e s,rai( Bacillus cereus =>) isola,ed from
<es, adar oil <ells i( ,he sou,h of ra(.
Moreo&er) a reso(se surfa%e me,hodolog <as
alied ,o de,ermi(e ,he aroria,e %o(di,io(s
of ,he ro%ess <i,h ma!imum desulfuri;a,io(.
ur,hermore) ,he ki(e,i% ra,e e!ressio( of ,he
D* rea%,io( for DT <as e&alua,ed.
EXPERIMENTALS
Materials and Methods
Chemicals
>ormal dode%a(e) DT) (u,rie(, agar) (u,rie(,
-ro,h) a(d ma,erials for reari(g ,he media
i(%ludi(g glu,ami% a%id) gl%erol) >a=24.=2)
G2=4) Mg7l2.6=2) 7a7l2.2=2) e7l#) a(d >=47l
<ere o-,ai(ed from Mer%k 7o. /Herma(0.
>u,rie(, -ro,h />0 is a mi%ro-iologi%al gro<,h
medium %ommo(l used for ,he rou,i(e %ul,i&a,io( of (o(fas,idious -a%,eria. , is also used as a
re%ul,ure medium for i(%reasi(g ,he (um-er of
,he %ells -efore ,ra(sferri(g ,hem ,o ,he
rodu%i(g medium. The %omosi,io( of ,he
medium is ".5? e,o(e) ".#? -eef e!,ra%,eas,
e!,ra%,) a(d ".5? >a7l. All ,he o,her %hemi%als
used i( ,he rese(, <ork <ere of a(al,i%al
grade. Deio(i;ed dis,illed <a,er <as also used ,o
reare all media a(d solu,io(s.
Microorganism
Isolation of DBT Desulfurizing Microorganisms
il samles <ere %olle%,ed from <es, adar oil
<ells i( ,he sou,h of ra() u(der ase,i% %o(di,io(s
- s,erile samli(g -o,,les. The() 1 ml of oil
samle <as fed i(,o a 25" ml flask %o(,ai(i(g 1""
ml (u,rie(, -ro,h medium a(d i(%u-a,ed a, ,<o
differe(, ,emera,ures) (amel #" a(d 4" 7)
<hile s,irri(g a, 1" rm for o(e <eek. The() ,he-a%,erial s,rai(s <ere urified a(d more ,ha(
,<e(, ,es of %olo(ies <ere urified.
Identification of Selective Strain
16* ri-o,i(g <as %arried ou, ,o ide(,if ,he
-a%,erium. The seue(%e a(alsis <as er
formed a, $i-osomal Da,a-ase ro3e%, /$D0 I
a(d ,he -asi% lo%al alig(me(, sear%h ,ool
/BA*T(0 a(alsis <as %o(du%,ed a, >a,io(al
7e(,er for io,e%h(olog (forma,io( />70
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Journal of Petroleumiodesulfuri;a,io( of *imula,ed Bigh, uel il J Science and Technology
Journal of Petroleum Science and Technology 2014) 4/10) 29#8 h,,:3s,.rii.ir
2"14 $esear%h (s,i,u,e of e,roleum (dus,r /$0
, +1
ser&er. The alig(me(, of ,he seue(%e <as
%arried ou, usi(g 7B*TABK rogram a, Euro
ea( ioi(forma,i%s si,e. These seue(%e da,a
ha&e -ee( su-mi,,ed ,o ,he He(a(k da,a-ases
u(der a%%essio( (um-er of '"5198.
Media
The medium %o(,ai(i(g 4 gr. of >a=24.=2) 4
gr. of G2=4) 2" gr. of glu,ami% a%id) ".6 gr. of
>=47l) "."245 gr. of Mg7l2.6=2) ".""1 gr. of
7a7l2.2=2) ".""1 gr. of e7l#) a(d 2" ml of
gl%erol as ,he %ar-o( sour%e <as dissol&ed i(
1""" ml of deio(i;ed dis,illed <a,er. The = of
,he medium <as ,he( ad3us,ed ,o usi(g 1 >
sodium hdro!ide solu,io(.
Analytical Methods
7ell %o(%e(,ra,io( <as de,ermi(ed usi(g o,i%al
de(si, &alue o-,ai(ed - a 7amse% se%,ro
ho,ome,er /Model M5"10 a, 6"" (m. DT
%o(%e(,ra,io( a(d ,he me,a-oli,es i( ,he
rea%,io( mi!,ures <ere de,e%,ed a(d measured
- a gas %hroma,ograh /H7) ,e H789"A)
Agile(,) *A0 euied <i,h a mass se%,ros
%o de,e%,or a(d a %aillar %olum( /#" m L
".#2 mmL".25 m) Agile(,) *A0. The i(3e%,or
,emera,ure <as se, a, 25" 7 <hile ,he ,em
era,ure rogram used <as 4" 7 for 1 mi()
follo<ed - a ram of 1" 7mi( ,o 12" 7) a(d a
se%o(d ram of 12 7mi( ,o 2#2 7 for 1 mi(.
=elium <as used as ,he mo-ile hase a, a flo<
ra,e of 1.# mlmi(. All ,he e!erime(,al da,a
reor,ed i( ,he rese(, <ork are ,he mea(
&alues of ,he e!erime(,al da,a o-,ai(ed from
,<o or ,hree e!erime(,s <i,h a mea( s,a(dard
de&ia,io( of 5?. Moreo&er) ,he ,o,al sulfur
%o(,e(, of rea%,io( mi!,ures a(d kerose(e <as
de,ermi(ed - a ,o,al sulfur a(al;er /EDN$0.
Determination of Appropriate Conditions
of BDS Process Using Response Surface
Methodology
$eso(se surfa%e me,hodolog /$*M0 is a
%olle%,io( of useful ma,hema,i%al a(d s,a,is,i%al
,e%h(iues for modeli(g ro-lems usi(g ua(
,i,a,i&e da,a o-,ai(ed from a (um-er of
aroria,e e!erime(,s. The desired reso(se
is i(flue(%ed - se&eral &aria-les a(d ,he
reso(se is o,imi;ed usi(g a( o-3e%,i&e
fu(%,io( C2". ( ,his regard) ,hree imor,a(,
arame,ers of D* ro%ess) i(%ludi(g -io%a,als,
%ell de(si, /AO %ellml0) oil hase fra%,io( /0)
a(d ,he i(i,ial DT %o(%e(,ra,io( /7) m<0
<ere %hose(. The() a %e(,ral %omosi,e desig(
<as alied ,o ,he o,imi;a,io( ro-lem. To
ha&e desig( oi(,s) <hi%h had (o de%imal) ,he
&alue of arame,er P i( ,he $*M <as %hose( ,o
-e 2. This e!erime(,al desig( i(%luded ,<e(,
e!erime(,s for e&alua,i(g ,he model %oeffi%ie(,s from <hi%h eigh, oi(,s of fa%,orial
desig() si! a!ial oi(,s) a(d a %e(,er oi(, <i,h
si! reli%a,io(s <ere o-,ai(ed. This reli%a,io(
a, ,he %e(,er oi(, allo<ed es,ima,i(g e!eri
me(,al error for a -e,,er fi,,i(g. The resul,s of
,he roosed se, of e!erime(,s are summari;ed
i( Ta-le 1.
RESULTS AND DISCUSSION
Identification of Strain HN
( ,he rese(, s,ud) 1 morhologi%all dis,i(%,
mi%ro-ial %olo(ies <ere isola,ed. (e of ,he
isola,es) i(i,iall (amed =>) had ,he ma!imum
desulfuri;a,io( a%,i&i, /65"? of DT0 a(d <as
fi(all %hose( for fur,her s,udies. The 16*
ri-o,i(g a(d BA*T( a(alsis of ,he 62 -ase
airs <ere erformed a, ,he >a,io(al 7e(,er for
io,e%h(olog (forma,io( />70 ser&er) <hi%h
%o(firmed ,he ide(,i, of orga(ism) i.e. a s,rai(
of Bacillus cereus %alled Bacillus cereus =>.
Bacillus cereus -elo(gs ,o ,he grou of
Baciliacea orga(isms) <hi%h are rod shaed)
sore formi(g) gramosi,i&e) a(d mo,ile. igure
1 sho<s ,he gro<,h of => s,rai( used i( ,he
rese(, s,ud.
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Journal of Petroleum
Science and Technology D. Ara-ia() =. >a3afi) . arhadi) a(d A. Molaei Dehkordi
Journal of Petroleum Science and Technology 2014) 4/10) 29#8 h,,:3s,.rii.ir
2"14 $esear%h (s,i,u,e of e,roleum (dus,r /$0
+2 ,
Ta!le 1- ./perimental runs proposed !y the 0S' method
$u(/A0: 7ell De(si,
/%ellml0 L1"
/0: il hase
fra%,io(
/70: (i,ial DT %o(%e(,ra,io(
/m<0Desulfuri;a,io( /?0
1 2 ".# 5"" 55.9
2 # ".5 5" 56.1
# 1 ".5 5" #.6
4 # ".5 5" 4.2
5 4 ". 1""" 56.4
6 # ".5 5" 69.9
2 ".# 1""" 58.#
8 # ".5 5" 5#.#
9 # ".5 5" 2.8
1" # ".5 25" #1.2
11 # ".5 5" #.6
12 2 ". 1""" 56.6
1# 4 ".# 1""" 42.9
14 5 ".5 5" 62.#
15 # ".5 125" 5.8
16 # ".9 5" 56.1
1 2 ". 5"" 52.8
18 4 ".# 5"" 58.9
19 4 ". 5"" 54.#
2" # ".1 5" 6".2
&igure 1- roth of Bacillus cereus #$ during
cultiation at +0 3C ./perimental conditions-
atmospheric pressure and incu!ator stirring at 150
rpm6
Effect of Parameters
( ,he $*M) effe%,i&e &aria-les a(d ,heir roer
ra(ge ha&e ,o -e k(o<(. Therefore) ,hree -asi%
arame,ers su%h as -io%a,als, %o(%e(,ra,io()
oil hase fra%,io() a(d i(i,ial DT %o(%e(,ra,io(
<ere %hose( C19) 21. The i(flue(%es of ,hese
arame,ers o( ,he desulfuri;a,io( of DT <ere
ss,ema,i%all e!ami(ed o(e a, a ,ime. All ,he
assas <ere %arried ou, i( 1"" ml Erle(meer
flasks. Dode%a(e a(d DT <ere used as ,he oil
sol&e(, a(d model sulfur %omou(d rese%,,i&el. The D* <ere %arried ou, - i(%u-a,i(g a,
#" 7 a(d 18" rm for 48 hrs.
Effect of Biocatalyst Cell Density
(e of ,he mos, imor,a(, arame,ers i( ,he
D* ro%ess is -io%a,als, %ell de(si,. A high
%ell de(si, %a( redu%e oera,i(g %os,s. Thus i, is
imor,a(, ,o de,ermi(e ,he ma!imum -io
%a,als, %ell de(si, C22. To e!ami(e ,his effe%,)
a (um-er of e!erime(,al ru(s <ere %arried ou,
"
".#
".6
".9
1.2
1.5
" 5 1" 15 2" 25 #"
7 / y g e n e m a n d 8 7 9
8 : 0 0 n m 9
Culti2ation time 8hr9
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Journal of Petroleumiodesulfuri;a,io( of *imula,ed Bigh, uel il J Science and Technology
Journal of Petroleum Science and Technology 2014) 4/10) 29#8 h,,:3s,.rii.ir
2"14 $esear%h (s,i,u,e of e,roleum (dus,r /$0
, ++
i( 1"" ml Erle(meer flasks <i,h oil hase
fra%,io( a(d DT i(i,ial %o(%e(,ra,io( of ".5 a(d
5"" m rese%,i&el. ( ,hese e!erime(,s) %ell
de(si, &aried from 1×1" ,o 5×1"
/%ellml0
<i,h 1×1" i(%reme(,s. The o-,ai(ed e!eri
me(,al resul,s are rese(,ed i( igure 2. As %a(
-e sse() higher desulfuri;a,io( %a( -e o-,ai(ed
a, higher %ell de(si,. This %ould -e due ,o ,he
i(%reased (um-er of %ells) a(d ,hus more
-io%a,als, -ei(g a&aila-le for DT mole%ules.
=o<e&er) a, a %ell de(si, larger ,ha( #×1"
/%ellml0) ,he er%e(,age of desulfuri;a,io( falls.
This %a( -e e!lai(ed - ,he mass,ra(sfer
limi,a,io(s a(d i(a-ili, of some %ells ,o -e i(
%o(,a%, <i,h ,he orga(i% hase. ( fa%,) ,he ra,ea, <hi%h DT %a( -e %o(&er,ed - %ells is higher
,ha( ,he mass ,ra(sfer ra,e of DT from ,he
orga(i% hase i(,o ,he %ells. Therefore) ,he mass
,ra(sfer of DT from orga(i% hase i(,o ,he %ells
%o(,rols ,he o&erall ro%ess. ( ,his regard) ,he
e!is,e(%e of a( o,imum &alue of ,he -io%a,als,
loadi(g has -ee( reor,ed i( ,he li,era,ure C2#)
24.
&igure 2- .ffect of cell density on the percentage of
desulfuri;ation ./perimental conditions- C <T=>00
ppm" 7&P=06>" atmospheric pressure" T =+0 3C" and
incu!ator stirring at 150 rpm6
Effect of Oil Phase Fraction (OFP)
D* is ,i%all k(o<( as a ,<ohase aueous
oil ro%ess due ,o ,he <a,er reuireme(, for
-io%a,als,s. Therefore) ,he reuired amou(, of
<a,er is a ke arame,erO ,o ,his e(d) ,he
i(flue(%e of ,he oil hase fra%,io( o( ,he de
sulfuri;a,io( fra%,io( <as %arefull s,udied. (
,he rese(, <ork) ,he fra%,io( of oil hase
&aried from ".1 ,o ".9 <hile ,he ,<o o,her
arame,ers <ere ke, %o(s,a(, /i.e.) C DT Q 5""
m a(d %ell de(si,Q #×1" %ellml0. The
e!erime(,al resul,s o-,ai(ed are rese(,ed i(
igure #. As %a( -e i(ferred from ,his figure) ,he
desulfuri;a,io( of DT de%reases as ,he &olume
er%e(,age of orga(i% sol&e(, i(%reases) <hi%h is
full i( agreeme(, <i,h o,her s,udies reor,ed i(
,he li,era,ure C1) 18) 25. This %a( -e due ,o ,he
high hdroho-i%i, of DT. , should -e (o,ed
,ha, ,he ,ra(sor, of DT mole%ules i(,o ,he oil
<a,er i(,erfa%e is esse(,ial for ,he desulfuri;a
,io( rea%,io(s.
&igure +- .ffect of oil phase fraction 87&P on the
percentage of desulfuri;ation ./perimental condi?
tions- C <T=>00 ppm" atmospheric pressure"
T =+0 3C" cell density=+
10@ 8cellml" and incu!ator
stirring at 150 rpm6
Effect of Initial DBT Concentration
The effe%,s of i(i,ial su-s,ra,e %o(%e(,ra,io( o(
,he er%e(,age of desulfuri;a,io( are sho<( i(
igure 4. Differe(, DT %o(%e(,ra,io(s from 25",o 125" m< <i,h a 25" m i(%reme(, <ere
reared) <hile ,he -io%a,als, %o(%e(,ra,io(
a(d ,he oil hase fra%,io( <ere se, ,o -e #×1"
/%ellml0 a(d ".1 rese%,i&el. igure 4 %learl
sho<s ,ha, <i,h a( i(%rease i( ,he DT %o(%e(
,ra,io( i(%reases ,he er%e(,age of desulfuri;a
,io( due ,o ,he e(ha(%eme(, i( ,he DT
diffusio( ,o ,he oil<a,er i(,erfa%e. , is <or,h
(o,i(g ,ha, ,his -eha&ior has -ee( re&iousl
reor,ed - o,her resear%hers usi(g &arious
"
1"
2"
#"
4"
5"
6"@"
" 1 2 # 4 5 6
e s u l f u r i ; a t i o n 8 B 9
Cell ensity 8cellml9 L 1"@
"
1"
2"
#"
4"
5"
6"
@"
" ".2 ".4 ".6 ".8 1
e s u l f u r i ; a t i o n 8 B 9
7&P
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Journal of Petroleum
Science and Technology D. Ara-ia() =. >a3afi) . arhadi) a(d A. Molaei Dehkordi
Journal of Petroleum Science and Technology 2014) 4/10) 29#8 h,,:3s,.rii.ir
2"14 $esear%h (s,i,u,e of e,roleum (dus,r /$0
+4 ,
,es of mi%roorga(isms C18) 21.
&igure 4- .ffect of initial <T concentration on the
percentage of desulfuri;ation ./perimental condi?
tions- 7&P=061" atmospheric pressure" T =+0 3C" cell
density=+
10@ cellml" and incu!ator stirring at 150
rpm6
Correlation of Experimental Data
The e!erime(,al resul,s <ere a(al;ed -
sof,<are Desig( E!er,R 8.".1 a%kage. E&alu
a,i(g ,he sig(ifi%a(, model) ,he mos, effe%,i&e
arame,ers a(d ,heir ossi-le i(,era%,io(s <ere
o-,ai(ed - usi(g ,he ,e%h(iue of a(alsis of
&aria(%e /A>SA0 as sho<( i( Ta-le 2.
A uadra,i% model %ould -e sui,a-le a(d)
,herefore) i, <as %hose( for ,he su-seue(,
a(alsis of ,he e!erime(,al da,a. As %a( -e
see( i( Ta-le 2) ,he o-,ai(ed e!erime(,al
resul,s i(di%a,e ,ha, redi%,a-ili, of ,he model
is a, a %o(fide(%e le&el of 91?. Therefore)
reso(se fu(%,io( redi%,io(s <ere i( reaso(
a-le agreeme(, <i,h ,he e!erime(,al da,a <i,h
a( R2 &alue of ".912) <hi%h %learl sho<ed ,ha,
less ,ha( 9? of ,he ,o,al &aria,io(s %ould (o, -ee!lai(ed - ,his model. Moreo&er) as ,he isher
,es, / &alue0 <as fou(d ,o -e 25. <i,h a
&er lo< ro-a-ili, &alue / &alue "."""10) ,he
uadra,i% regressio( model %ould -e &alid. This
i(di%a,ed ,ha, o(l "."1? of ,he model
redi%,io(s <ere due ,o ,he (oise. The redi%,edR
2 &alue of ".5# is i( reaso(a-le agreeme(,
<i,h ,he ad3us,ed &alue of ".86". ( addi,io()
,he &alue of adeua,e re%isio( of reso(se)
<hi%h <as 21.185 /larger ,ha( 40) i(di%a,ed ,ha,
,he model %ould -e aroria,e for des%ri-i(g
,he rese(, D* ro%ess. The fi(al %orrela,io(
o-,ai(ed for ,he rese(, er%e(,age of de
sulfuri;a,io( %a( -e e!ressed -:
2 2
(%) 56.48 1.57
4.74 4.99 6.34 2.56
Desulfurization A
B C A B
= + −
+ − +
/10
<here) A) B) a(d C are ,he %ell de(si,) oil hase
fra%,io() a(d ,he i(i,ial DT %o(%e(,ra,io(
rese%,i&el.
igure 5 sho<s ,he ari, lo, of ,he
e!erime(,al a(d redi%,ed &alues of ,he
er%e(,age of desulfuri;a,io(. , is see( ,ha, ,he
redi%,ed a(d e!erime(,al &alues are dis,ri-
u,ed %lose ,o ,he diago(al li(e sho<i(g a
reaso(a-le agreeme(, -e,<ee( ,he redi%,ed
a(d e!erime(,al &alues of ,he er%e(,age of
desulfuri;a,io(. 7o(sideri(g Eua,io( 1) ,he
sig(ifi%a(, ,erms are ,hree li(ear effe%,s of all
,he arame,ers a(d ,he (o(li(ear effe%,s of ,he
-io%a,als, %ell de(si, a(d ,he oil hase
fra%,io(. ur,hermore) ,here are (o i(,era%,io(s
-e,<ee( ,he arame,ers -e%ause all ,he ossi
-le effe%,s of a( ,<o arame,ers are (o,sig(ifi%a(,.
Ta!le 2- 0esults of A$7CA
Source Sum of SDuares egree of &reedom 'ean SDuare & alue p?alue pro!E &
Model 225.24 5 445."5 25. "."""1
$esidual 241.8# 14 1.2
Ba%k of fi, 2"2.2 9 22.4 2.8# ".1#2
ure error #9.6# 5 .9#
R2
Q ".912") Ad3R2
Q ".86") reR2
Q ".5#) Adeua,e re%isio(Q 21.185
"
2"
4"6"
8"
1""
" 2"" 4"" 6"" 8"" 1""" 12"" 14""
e s u l f u r i ; a t i o n 8 B 9
<T concentration 8ppm9
8/11/2019 03 1080 rev. 5 ver 2.0.0
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Journal of Petroleumiodesulfuri;a,io( of *imula,ed Bigh, uel il J Science and Technology
Journal of Petroleum Science and Technology 2014) 4/10) 29#8 h,,:3s,.rii.ir
2"14 $esear%h (s,i,u,e of e,roleum (dus,r /$0
, +>
&igure >- Predicted ersus actual alues of the
percentage of desulfuri;ation ./perimental condi?
tions- atmospheric pressure" T =+0 3C" and incu!ator
stirring at 150 rpm6
Optimization of Desulfurization
The o,imi;a,io( of ,he rese(, D* ro%ess for
o-,ai(i(g ,he er%e(,age of ,he ma!imum
-iodesulfuri;a,io( <as erformed. To ,his e(d)
,he o,imum %o(di,io(s of ,he D* <ere
de,ermi(ed as follo<s: -io%a,als, %ell de(si,Q
#.6×1" /%ellml0) oil hase fra%,io(Q ".2) a(d
i(i,ial DT %o(%e(,ra,io(Q 1"86 m<O ,hese
%o(di,io(s ro&ided a er%e(,age of desulfuri;a
,io( of ".91. Moreo&er) ,he o,imum %o(di
,io(s redi%,ed - $*M <ere also &erified -
%arri(g ou, ,hree addi,io(al e!erime(,s. This
amou(, of oil hase fra%,io( a, ,he o,imum
%o(di,io(s ro&ides a grea, ad&a(,age. , should
-e (o,ed ,ha, fe< mi%roorga(isms <ere a-le ,o
ro&ide a high er%e(,age of desulfuri;a,io( of
DT a, oil hase fra%,io(s larger ,ha( ".1. This
fi(di(g %a( -e &er imor,a(,) -e%ause o(e of
,he esse(,ial ro-lems of i(dus,rial D* ro%ess
is ,he large &olume of <a,er.
Kinetic Rate Expression
The -io%a,als, <hi%h <as i( ,he s,a,io(ar
hase <as used ,o e&alua,e ,he ki(e,i% ra,e
e!ressio(. ( fa%,) -io%a,als, %o(%e(,ra,io(
remai(ed almos, u(%ha(ged duri(g ,he rea%,io(
,ime. The arame,ers of ro%ess <ere se, a,
o,imum %o(di,io(s es,ima,ed - $*M. The()
,he effe%,s of oera,i(g ,emera,ure o( ,he
desulfuri;a,io( <ere e!ami(ed. These e!eri
me(,al resul,s are sho<( i( igure 6.
&igure :- .ffect of temperature on the percentage of
desulfuri;ation ./perimental conditions- C <T=>00
ppm" atmospheric pressure" T =+0 3C" 7&P=061" cell
density=+
10@ 8cellml" and incu!ator stirring at
150 rpm6
The ge(eral n,horder o<erla< rea%,io( ra,e
e!ressio( <as %hose( ,o %orrela,e ,he e!eri
me(,al da,a. , <as fou(d ,ha, ,he -es, &alue of
n for ,his ro%ess %ould -e 1. Therefore) ,he ra,e
e!ressio( for ,he D* of DT %a( -e e!ressed
as:
DBT DBT
dC kC
dt
−= /20
12.792.715expk
R T
− =
/#0
<here) C DT) t ) a(d k are DT %o(%e(,ra,io(
/m<0) ,ime /hr0) a(d rea%,io( ra,e %o(s,a(,
/hr1
0 rese%,i&el. R a(d T rerese(, ,he u(i&er
sal gas %o(s,a(, /k'mol.G0 a(d ,emera,ure /G0
rese%,i&el. The %omariso( of DT degrada
,io( e!erime(,al resul,s a(d ,hose redi%,ed -
,he firs,order rea%,io( ra,e e!ressio( is sho<(i( igure . The mea( a-solu,e de&ia,io( of ,he
model redi%,io(s from ,he e!erime(,al da,a is
5?. Moreo&er) e&alua,i(g ,he %orrela,io( -e
,<ee( ,emera,ure a(d ,he er%e(,age of de
sulfuri;a,io( sho<s a grea, ad&a(,age. This
mi%roorga(ism is a-le ,o desulfuri;e DT o&er
,he ,emera,ure ra(ge of #" ,o 4" 7O addi,io(
all) a( i(%rease i( ,he rea%,io( ,emera,ure
i(%reases ,he degrada,io( of DT as ,he model
sulfur %omou(d. Thus ,he sulfur%o(,ai(i(g
25."
#5."
45."
55."
65."
@5."
25." #5." 45." 55." 65." @5." 85."
e s u
l f u r i ; a t i o n 8 B 9 "
P r e d i c t e d
esulfuri;ation 8B9" Actual "
2"
4"
6"
8"
" 12 24 #6 48 6" @2 84
e s u l f u r i ;
a t i o n 8 B 9
t 8hr9
#"
#5
4"
Tem+era,ure /70
8/11/2019 03 1080 rev. 5 ver 2.0.0
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Journal of Petroleum
Science and Technology D. Ara-ia() =. >a3afi) . arhadi) a(d A. Molaei Dehkordi
Journal of Petroleum Science and Technology 2014) 4/10) 29#8 h,,:3s,.rii.ir
2"14 $esear%h (s,i,u,e of e,roleum (dus,r /$0
+: ,
s,reams do (o, (eed a( e!,ra %ooli(g ,o ,emer
a,ure lo<er ,ha( 4" 7. Therefore) ,his ,hermo
hili% -a%,erium %a( -e ui,e romisi(g.
&igure @- Comparison of the <T degradation
e/perimental data ith those predicted !y first?
order reaction rate e/pression ./perimental condi?
tions- C <T=105: ppm" atmospheric pressure"
T = 40 3C" cell density=+
10@ 8cellml" 7&P=061" and
incu!ator stirring at 150 rpm6
Desulfurization of Kerosene
i(all) ,he -iodesulfuri;a,io( of kerose(e)
<hi%h has some similari, <i,h ,he simula,ed
ligh, fuel oil) <as %arried ou, ,o e&alua,e ,he
%aa-ili, of ,his mi%roorga(ism ,o degrade real
oil samles. The -io%a,als, %ell de(si, a(d oil
hase fra%,io( <ere %hose( a%%ordi(g ,o ,he
o,imum %o(di,io(s o-,ai(ed - $*M) <hile ,he
i(i,ial ,o,al sulfur %o(,e(, of kerose(e <as 2###
m<. The roer,ies of kerose(e rodu%ed -
sfaha( refi(er used i( ,he rese(, s,ud are
summari;ed i( Ta-le #. As %a( -e (o,i%ed) ,he
ra(ge of -oili(g oi(, of ,he kerose(e used is
15"22 7. The mai( sulfur %omou(ds of fueloil i( ,he kerose(e -oili(g ra(ge are -e(;o,hio
he(e a(d i,s alkla,ed deri&a,i&es. The H7M*
a(alsis %o(firmed ,he rese(%e of -e(;o,hio
he(e a(d i,s alkla,ed deri&a,i&es su%h as 5
me,hl -e;o,hiohe(e a(d #me,hl -e(;o,hio
he(e i( ,he rese(, kerose(e. esides) some
o,her sulfur %omou(ds su%h as 1dode%a(e
,hiol <ere also o-ser&ed i( ,he kerose(e. Af,er
2 hr) ,he ,o,al sulfur %o(,e(, of kerose(e <as
redu%ed ,o 155 m. 7o(sideri(g ,he high
i(i,ial ,o,al sulfur %o(,e(, of kerose(e) i, seems
,ha, ,his mi%roorga(ism %ould -e romisi(g for
,he desulfuri;a,io( of DTO ho<e&er) i, ro-a-l
does (o, ossess ,he a-ili, ,o desulfuri;e o,her
,es of sulfur%o(,ai(i(g %omou(ds.
Ta!le +- Properties of (erosene feedstoc(
Property
alue
De(si, /kgm#0 95
Sis%osi, a, 2" 7 /ma.s0 1.46
Aroma,i% %o(,e(, /Sol.?0 18
To,al a%id (um-er /mg G=g0 "."18
(i,ial -oili(g oi(, /...0) 7 1#
5? 19
1"? 18#
#"? 195
5"? 2"9
"? 225
9"? 245
95? 254
i(al -oili(g oi(, /...0) 7 269
CONCLUSIONS
( ,he rese(, <ork) a( e!erime(,al i(&es,iga
,io( <as %o(du%,ed o( ,he -iodesulfuri;a,io( of
a model solu,io( of DT as <ell as u(,rea,ed
kerose(e <i,h a high ,o,al sulfur %o(,e(, -
usi(g a (a,i&e isola,ed -a%,eria Bacillus cereus
=>. The effe%,s of &arious oera,i(g arame,ers
o( ,he desulfuri;a,io( of DT <ere e!ami(ed. ,
<as fou(d ou, ,ha,:
1
The remo&al of DT from ,he model solu,io( /DT i( dode%a(e0 %a( -e %arried ou,
- ,his ,e of mi%roorga(ism. The ield of
D* i(%reases <i,h a( i(%rease i( ,he %ell
de(si, u ,o #×1") a de%rease i( ,he )
a(d a( i(%rease i( ,he i(i,ial DT %o(%e(
,ra,io(.
2 DT %a( -e desulfuri;ed from ,he model
solu,io( <i,h a( aroria,e amou(, of
-io%a,als, %ell de(si, a(d a, rela,i&el
lo< ,emera,ure a(d a,mosheri% res
"
2""
4""
6""
8""
1"""
12""
" 2" 4" 6" 8"
< T c o n c e n t r a t i o n 8 p p m
9
t 8hr9
redi%,ed 7o(%e(,ra,io( -Gi(e,i% EAua,io(
E!+erime(,al $esul,s
Tem+era,ureQ 4" /°70
8/11/2019 03 1080 rev. 5 ver 2.0.0
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Journal of Petroleumiodesulfuri;a,io( of *imula,ed Bigh, uel il J Science and Technology
Journal of Petroleum Science and Technology 2014) 4/10) 29#8 h,,:3s,.rii.ir
2"14 $esear%h (s,i,u,e of e,roleum (dus,r /$0
, +@
sure. Moreo&er) -iodesulfuri;a,io( of DT
o-es ,he seudofirs,order ra,e e!res
sio( i( ,erms of sulfur %o(%e(,ra,io(.
# (,rea,ed kerose(e <i,h a high ,o,al sulfur
%o(,e(, i( %omariso( <i,h DT %ould also
-e sligh,l desulfuri;ed.
4 The resul,s of ,he $*M sho<ed ,ha, a
uadra,i% %orrela,io( %ould -e roosed for
,he i(flue(%es of -io%a,als, %ell de(si,)
) a(d ,he i(i,ial DT %o(%e(,ra,io( o(
,he desulfuri;a,io( of DT.
ACKNOWLEDGEMENT
The au,hors are &er gra,eful for ,he fi(a(%ial
suor, ro&ided - *harif (i&ersi, of Te%h(olog /Tehra() ra(0.
NOMENCLATURE
D* iologi%al desulfuri;a,io(
BA*T( asi% lo%al alig(me(, sear%h ,ool
DT Di-e(;o,hiohe(e
... i(al -oili(g oi(,
H7 Has %hroma,ograh
=D* =drodesulfuri;a,io(... (i,ial -oili(g oi(,
>7 >a,io(al %e(,er for -io,e%h(olog
i(forma,io(
D !ge( dema(d
il hase fra%,io(
$*M $eso(se surfa%e me,hodolog
$D $i-osomal da,a-ase ro3e%,
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8/11/2019 03 1080 rev. 5 ver 2.0.0
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