Jpst 2014 Vol. 4 No. 1

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Research Institute ofPetroleum Industry

Director in Charge

Vahid Haddadi-Asl

Editor in Chief

Vahid Haddadi-Asl

Editors

Mohammad Reza Jafari Nasr

Ali-Akbar Safekordi

Associate Editor

Mohammad Najafi

JJJOOOUUURRR NNN A A ALLL OOOFFF PPPEEETTTRRROOOLLLEEE UUUMMM

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ISSN: 2251-659X

Vol !" No 1" 2#1!

Accredited by the Ministry of Science, Research, and Technology

Accreditation Number: 192255

Accredited on: A!ril 1, 2"1#

Accreditation $eriod: A!ril 2"11 to A!ril 2"15

Editorial BoardH. R. Aghabozorg, Associate Professor of hemistr! at Research "#stit$te of Petrole$m "#d$str!

H. Arabi, Associate Professor of Pol!mer %#gi#eeri#g at "ra# Pol!mer a#d Petrochemical "#stit$te

&. 'asta#i, Professor of hemical %#gi#eeri#g at Sharif (#i)ersit! of *ech#olog!

V. Haddadi-Asl, Professor of Pol!mer %#gi#eeri#g at Amirkabir (#i)ersit! of *ech#olog!

M. R. Jafari Nasr, Associate Professor of hemical %#gi#eeri#g at Research "#stit$te of Petrole$m "#d$str!

M. Jamialahmadi, Professor of Petrole$m %#gi#eeri#g at Ah+az Petrole$m (#i)ersit! of *ech#olog!

M. R. amali, Associate Professor of Petrole$m eolog! a#d eochemistr! at Research "#stit$te of Petrole$m "#d$str!

M. Masihi, Associate Professor of Petrole$m %#gi#eeri#g at Sharif (#i)ersit! of *ech#olog!H. Modares, Professor of hemical %#gi#eeri#g at Amirkabir (#i)ersit! of *ech#olog!

M. Mohammadzadeh Attar, Associate Professor of olor %#gi#eeri#g at Amirkabir (#i)ersit! of *ech#olog!

S. R. Mo$sa)i Harami, Professor of Petrole$m eolog! at erdo+si (#i)ersit! of Mashhad

&. Mo+la, Professor of hemical %#gi#eeri#g at Shiraz (#i)ersit!

M. Nasr %sfaha#!, Professor of hemical %#gi#eeri#g at "sfaha# (#i)ersit! of *ech#olog!

M. Nekooma#esh, Professor of Pol!mer hemistr! at "ra# Pol!mer a#d Petrochemical "#stit$te

M. R. /midkhah, Professor of hemical %#gi#eeri#g at *arbiat Modares (#i)ersit!

. Rashidi, Professor of Petrole$m a#d as %#gi#eeri#g at Amirkabir (#i)ersit! of *ech#olog!

A. A. Safekordi, Professor of hemical %#gi#eeri#g at Sharif (#i)ersit! of *ech#olog!

J. *o+fighi, Professor of hemical %#gi#eeri#g at *arbiat Modares (#i)ersit!

%. Vashegha#i araha#i, Professor of 'io0ol!mer %#gi#eeri#g at *arbiat Modares (#i)ersit!

M. Voso$ghi, Professor of 'iochemical %#gi#eeri#g at Sharif (#i)ersit! of *ech#olog!

Sh. Voso$ghi, Professor of Petrole$m %#gi#eeri#g at a#sas (#i)ersit!

Typesetting Team

M. hazrae!a# Vafadar

N. &eldar

*. Moradia#

P. No$ri

h. %1tesad

M. H. 2areia#

Contact Information

Research "#stit$te of Petrole$m "#d$str! 3R"P"4, 5est 'l)d.

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SSSCCCIIIEEENNNCCCEEE A A A NNNDDD TTTEEECCCHHH NNNOOOLLL OOOGGG Y Y Y

Vol !" No 1" 2#1!

ISSN: 2251-659X

TABLE OF COTET!

Diagenesis and Reser"oir #uality E"olution of !helf$margin !andstones in Pearl

Ri"er %outh Basin& !outh China !ea '($()C. he#gf$, . $oj$#, &. $ichao, 2. o#gche#g, 2. She#g, a#d C. hao

In !itu !ilica !upported %etallocene Catalysts for Ethylene Polymeri*ation+'$+,

S. Ahmadjo, H. Arabi, h. H. 2oh$ri, h. R. Nejabat, M. /mid)ar, M. Ahmadi, a#d S. M.

M. Mortaza)i

Biodesulfuri*ation of !imulated Light Fuel Oil -y a ati"e Isolated Bacteria

Bacillus Cereus .+)$/,

&. Arabia#, H. Najafi, . arhadi, a#d A. Molaei &ehkordi

De"eloping a e0 Initiali*ation Procedure for Distillation Column !imulation /)$11

J. ")ak0o$r a#d N. asiri

Core Flood !tudies to E"aluate Efficiency of Oil Reco"ery -y Lo0 !alinity 2ater

Flooding as a !econdary Reco"ery Process13$31

S. Shaddel, M. Hemmati, %. 2ama#ia#, a#d N. Nejati Moharrami

A Rigorous Comparison of %ethods for %ulti$0alled Car-on anotu-es

Purification 4sing Raman !pectroscopy33$5'

R. Cotfi, A. M. Rashidi, a#d M. Mohse##ia

An E6perimental In"estigation of 7ra"ity Drainage During Immisci-le 7as

In8ection in Car-onate Roc9s under Reser"oir Conditions5($5)

R. Par)izi a#d %. hasemi Nejad

An Optimi*ation Approach to Refinery !team %anagement 0ith Consideration

of CO+ Emission:'$,(

M. R. Jafari Nasr, M. Amid0o$r, a#d H. hodaei

8/11/2019 Jpst 2014 Vol. 4 No. 1


Journal of PetroleumScience and Technology

*Corresponding author

Chen Guojun

Email: [email protected]

Tel: +86 931 496 0908

Fa: +86 931 496 0916

Article history

!ecei"e#: $anua%& 0'( '013

!ecei"e# in %e"i)e# *o%m: c,obe% 08( '013

-cce,e#: /o"embe% 18( '013

-"ailable online: a%ch 10( '014

Journal of Petroleum Science and Technology 2014 , 412( 0119 h,,:j),.%ii.i%

5 '014 !e)ea%ch n),i,u,e o* 7e,%oleum n#u),%& !72

1

DIAGENESIS AND RESERVOIR QUALITY EVOLUTION OF SHELF-

MARGIN SANDSTONES IN PEARL RIVER MOUTH BASIN, SOUTH

CHINA SEA

Lyu Chengfu1 Chen !uo"un

1* #u !uichao

12 $hang !ongcheng

% $heng Sheng

12 and Li Chao

12

1e& abo%a,o%& o* 7e,%oleum !e)ou%ce) !e)ea%ch( n),i,u,e o* Geolog& an# Geoh&)ic)( Chine)e -ca#em& o*

cience)( anzhou ;30000( China'

<ni"e%)i,& o* Chine)e -ca#em& o* cience)( =eijing 100049( China3

!e)ea%ch n),i,u,e o* China /a,ional **)ho%e il Co%o%a,ion( =eijing 1000';( China

ABSTRACT

- ),u#& o* ,he #iagene,ic e"olu,ion o* )an#),one) *%om 7an&u lo>uli*, in ,he 7ea%l !i"e% ou,h

=a)in >a) ca%%ie# ou, ,o un%a"el ,he con,%ol) on )hel* ma%gin )an#),one %e)e%"oi% ?uali,&. The

%e)e%"oi% %oc)( ligocene "olcanic cla),ic )an#),one) o* ,he Ahuhai Fo%ma,ion( ha"e a bu%ial #e,h

o* ';6B ,o 3440 m. ;0 )amle) >e%e ),u#ie# u)ing ,he g%anulome,%ic anal&)e)( %a& #i**%ac,ion

!D2 anal&)e)( o%o)i,& an# e%meabili,& mea)u%emen,)( E ob)e%"a,ion)( an# me%cu%&

o%o)ime,%& mea)u%emen,). The )an#),one) a%e *ine ,o me#iumg%aine# li,hic )uba%o)e( )ub

li,ha%eni,e( an# )uba%o)e >i,h an a"e%age *%ame>o% como)i,ion o* ;'F131B. igh con,en, an#

),%ongl& al,e%e# "olcanic %oc *%agmen,) a%e ,he mo), imo%,an, #e,%i,al comonen,). n ,hi) >o%(

,&ical #iagene,ic %oce))e) )uch a) comac,ion( !F "olcanic %oc *%agmen,)2 an# *el#)a%

#i))olu,ion( ca%bona,e cemen,)( ?ua%,z o"e%g%o>,h( an# cla& cemen,) a%e ob)e%"e#. Cemen,) in

eo#iagene)i) ),age mainl& inclu#e cla& coa,ing( ea%l& calci,e an# )i#e%i,e. The main me)ogene,iccemen,) inclu#e aolini,e( ane%i,e( an# mino% ?ua%,z. The #i))olu,ion o* !F( *el#)a%( an#

ca%bona,e cemen,) i) ,he mo), #i),ingui)hing *ea,u%e >hich ha# con,%olle# o%o)i,& an#

e%meabili,&. Ca%bon an# o&gen i)o,oe) >e%e mea)u%e# ,o #i)cu)) ,he ca%bon )ou%ce) *o%

%ecii,a,ion an# #iagene,ic ,eme%a,u%e) o* ca%bona,e cemen,) e,en)i"el& #e"eloe# in )amle#

in,e%"al). 7o%e ,&e) in ,he anal&ze# )amle) change *%om a mi o* %ima%& ,o )econ#a%& o%e).

7%ima%& o%e) ha"e been #e),%o&e# b& mechanical comac,ion o% occlu#e# b& ?ua%,z( cla&( an#

ca%bona,e cemen,). econ#a%& o%e) >e%e gene%a,e# b& ,he #i))olu,ion o* !F an# *el#)a%)

#u%ing bu%ial hi),o%&. ,) "olume "a%ie# *%om ,%ace ,o 8H an# g%ea,l& im%o"e# ,he o%o)i,& o*

)an#),one) >i,h inc%ea)ing bu%ial #e,h. 7o%o)i,& "a%ie) *%om 4 ,o '0H in ,hi) >o% an# i) ,he

highe), *o% ,he )amle) >he%e ca%bona,e cemen, con,en,) a%e lo> an# #i))olu,ion i) >ell

#e"eloe#.

&ey'ords: an#),one Diagene)i)( !e)e%"oi% uali,&( Ca%bona,e Cemen,( Comac,ion( 7an&u o>

uli*,( 7ea% !i"e% ou,h =a)in

8/11/2019 Jpst 2014 Vol. 4 No. 1


Journal of Petroleum

Science and Technology . Cheng*u( C. Guojun( D. Guichao( A. Gongcheng( A. heng( an# . Chao

Journal of Petroleum Science and Technology 2014( 412( 0119 h,,:j),.%ii.i%


2 (

INTRODUCTION

The 7an&u lo>uli*, i) one o* ,he mo),

imo%,an, oil %o#uc,ion an# e,%oli*e%ou) a%ea)

in 7ea% !i"e% ou,h =a)in. , lie) on ,he )hel* o*

ou,h China ea >i,h a >a,e% #e,h o* le)) ,han

300m. e"e%al ga) *iel#) >e%e #i)co"e%e# in ,hi)

a%ea )ince '001 I1J( in#ica,ing ,ha, ,he 7an&u

lo>uli*, ha) g%ea, h&#%oca%bon o,en,ial I'J.

-l,hough big %og%e)) >a) ma#e in oilga)

elo%a,ion)( limi,e# #%illing) >e%e ca%%ie# ou, in

,he ),u#ie# a%ea an# no>le#ge o* #iagene)i)(

e,%oh&)ical %oe%,ie)( o%o)i,& e"olu,ion( an#

con,%ol) o* #iagene)i) on %e)e%"oi% ?uali,& i) ),ill

limi,e#. o( ,he ),u#& o* %e)e%"oi% cha%ac,e%iza

,ion in %e)e%"oi% )an#),one) in 7an&u lo>uli*,

i) nece))a%&.

!e)e%"oi% ?uali,& a))e))men, i) one o* ,he e&

elemen,) on ,a%ge, )an#),one %e)e%"oi% %o)ec

,i"e,& #u%ing h&#%oca%bon elo%a,ion) I3;J.

De,aile# un#e%),an#ing o* %e)e%"oi% ?uali,& an#

*ac,o%) ,ha, con,%ol %e)e%"oi% ?uali,& i) imo%

,an, an# e))en,ial ,o a))i), >i,h ,he %e)e%"oi%

?uali,& %e#ic,ion an# e,%oleum elo%a,ion)

I811J. n ,hi) ),u#&( a )ui,e o* #el,aic )an#),one)

*%om *ou% >ell) o* 7an&u lo>uli*, in ,he 7ea%l

!i"e% ou,h =a)in >a) in"e),iga,e# >i,h aiming

,o eamine ,he #iagene,ic *ea,u%e) #u%ing

bu%ial( #e)c%ibing %e)e%"oi% ?uali,& cha%ac,e%

i),ic)( anal&zing o%o)i,& e"olu,ion( an# #e,e%

mining *ac,o%) ,ha, con,%ol )hel*ma%gin )an#

),one) %e)e%"oi% ?uali,&. Ke hoe ,ha, ,he

be,,e% un#e%),an#ing o* ,he %e)e%"oi% ?uali,& in

,he )hallo> >a,e% a%ea o* ,he 7an&u lo>uli*,coul# hel *u%,he% elo%a,ion in ,hi) a%ea an#

gi"e an in)igh, in,o ,he a#jacen, #ee >a,e%

%o)ec,) o* ,he a#jacen, =ai&un ag in Ahu

#e%e))ion.

EXPERIMENTAL

Geological Setting

The 7ea%l !i"e% ou,h =a)in 7!=2 i) a a))i"e

con,inen,al ma%gin ba)in an# i) como)e# o*

,h%ee )ubba)in) I1'14J( inclu#ing ,he Ahu

#e%e))ion( ,he Ahu #e%e))ion( an# ,he Ahu

#e%e))ion. , i) loca,e# in ,he no%,he%n

con,inen,al )hel* o* ,he ou,h China ea(

co"e%ing abou, 1;.BL104

m'

. The geologicale"olu,ion o* ,he ba)in can be #i"i#e# in,o ,h%ee

main ,ec,onic ),age)( namel& 12 %i*,ing ),age in

,he la,e C%e,aceou) e%io#,he ea%l& ligocene

Eoch( '2 #e%e))ion ),age #u%ing ,he la,e

ligocene,he ea%l& iocene( an# 32 bloc

*aul,ing ),age *%om ,he la,e iocene ,o ,he

%e)en, I1'J.

The ),u#& a%ea( 7an&u lo>uli*,( i) )i,ua,e# in

,he mi##le o* 7!= I1B(16J. , lie) in ,he mi##le

a%, o* C<= an# i) boun#e# b& =ai&un ag in Ahu

#e%e))ion ,o ,he )ou,h an# Ahu #e%e))ion

,o ,he no%,h Figu%e 12. -"e%age >a,e% #e,h i)

'00 m. Eigh, *o%ma,ion) *%om ,he bo,,om ,o ,he

,o ha"e been %ecognize# Figu%e '2. The bu%ial

an# ,he%mal hi),o%ie) o* ,he )an#),one) *%om

7an&u lo>uli*, i) )ho>n in Figu%e 3. Ga)

%e)e%"oi%) a%e #e"eloe# mainl& in Ahujiang(

anjiang( an# Muehai *o%ma,ion I1;J. Thic an#

e,en)i"el& #i),%ibu,e# lacu),%ine mu#),one in,he Eoceneligocene ha) been i#en,i*ie# a) ,he

main )ou%ce %oc in ,he a#jacen, =ai&un )ag

I16(18(19J. The%e a%e *ou% imo%,an, Cenozoic

,ec,onic e"en,) in ,he #e"elomen, an# e"olu

,ion o* 7an&u lo>uli*,:

12 Ea%l& Eocenemi##le Eocene. -**ec,e# b& ,he

*i%), ei)o#e o* Ahu?iong mo"emen,( ,he )ou,h

o* 7!= ee%ience# ),%ong %i*,ing an# a )e%ie)

o* )ea%a,e #ee )ubba)in) >e%e *o%me#. n,hi) ),age( Kencang *o%ma,ion in ,he 7an&u lo>

uli*, >a) #eo)i,e# an# mainl& cha%ac,e%ize#

b& ,he #eo)i,) o* allu"ial *an*lu"iallae *acie).

'2 i##le Eoceneea%l& ligocene. -**ec,e# b&

,he )econ# ei)o#e o* Ahu?iong mo"emen,( ,he

7!= >a) uli*, an# *u%,he% e,en)ionall&

*aul,e#. The a%ea o* lacu),%ine ba)in ean#e# in

,hi) e%io# an# Ening *o%ma,ion >a) #eo)i,e#N

,he )e#imen,a%& en"i%onmen,) a%e ),%eam lain

8/11/2019 Jpst 2014 Vol. 4 No. 1


Journal of PetroleumDiagene)i) an# !e)e%"oi% uali,& E"olu,ionO Science and Technology



( %

#el,alae *acie) in 7an&u lo>uli*,. The ),%a,a

o* Ening *o%ma,ion a%e al)o imo%,an, )ou%ce

%oc) in 7!=.

32 a,e ligocenemi##le iocene( /anhai

mo"emen,( ,he ),%onge), ,ec,onic mo"emen,,ha, 7!= ee%ience#( cau)e# %egional u

li*,ing an# e%o)ion( %e)ul,ing in %egional uncon*o%

mi,& in 7!=. n ,hi) ),age( >a,e% le"el became

)hallo>e% an# Ahuhai *o%ma,ion >a) #eo)i,e#N

,he )e#imen,a%& en"i%onmen,) a%e #el,a( li,,o%al

*acie). The )ea *loo% o* ou,h China ea )%ea# in

abou, 30 illion &ea%) an# >a) al)o a**ec,e# b&

,he global inc%ea)e o* )ea le"el. 7!= en,e%e# an

en,i%e )ub)i#ence ),age an# #eo)i,e# ,hic

),%a,a o* Ahujiang *o%ma,ionN ,he )e#imen,a%&

en"i%onmen,) a%e mainl& #el,a( )hallo> ma%ine

*acie). !ee*)( )hoal( an# ca%bona,e %oc) >e%e

#e"eloe# on ,he ma%gin o* uli*,) o% la,*o%m).

42 i##le iocenela,e iocene. -**ec,e# b&

Dong)ha mo"emen,( ,he a%ea >a) comle,el&

co"e%e# a, ,hi) ),age. Deo)i,) o* anjiang

Muehai *o%ma,ion in ,he no%,h #e%e))ion zone

o* 7!= a%e mainl& #el,ane%i,ic *acie)( >hile

con,inen,al )hel*ue% ,o con,inen,al )loe

#eo)i,) a%e %e)en, in ,he )ou,h #e%e))ion

zone.

)igure 1 Location map of the Pear +i,er -outh .asin and the 'ells included in this study/ P+-. Pearl +i,er

-outh .asin #. iongdongnan .asin $hu 3 $hu 3 #epression $hu 33 $hu 33 #epression $hu 333 $hu 333

#epression . orthern plift .elt C. Central plift .elt S. Southern plift .elt .S .aiyun Sag 5167/

8/11/2019 Jpst 2014 Vol. 4 No. 1






4 (

)igure 2 !enerali8ed stratigraphic column of the Pearl +i,er -outh .asin modified from $hang et al/ 517

)igure % #iagram of 9urial:thermal history and time of hydrocar9on fillings for Panyu lo':uplift ;modified

after Pang et al/</ =P =nping $> $huhai $J $hu"iang >J >an"iang ?> ?uehai @S @anshan 57/

8/11/2019 Jpst 2014 Vol. 4 No. 1





( 6

Samples and Methodology

- ,o,al o* ;0 co%e )amle) *%om Ahuhai

*o%ma,ion in *ou% >ell) in ,he ),u#ie# a%ea

inclu#ing 1B )amle) *%om >ell 7M341'

3348.633386 m2( B )amle) *%om >ell 7M';'1

30'8.B3034.6 m2( 'B )amle) *%om >ell 7M';

11 ';6B.B';83.06 m an# 3''1.;3'44.;8 m2(

an# 19 )amle) *%om >ell 7M3311 3401.B4

3438.'m2 >e%e ,aen *%om ,he main %e)e%"oi%

in,e%"al). =e*o%e )amling( ,he #e,aile# ob)e%"a

,ion an# #e)c%i,ion o* co%e) >e%e ca%%ie# ou,.

The )amle) >e%e im%egna,e# >i,h blue #&e

%e)in be*o%e ,hin )ec,ion %ea%a,ion ,o highligh,

o%o)i,& an# a))i), ,he ob)e%"a,ion o* o%e ,&e)(*ea,u%e)( #i),%ibu,ion( an# %ela,ion)hi >i,h

*%ame>o% g%ain). Thin )ec,ion) >e%e ),aine#

>i,h ,he mie# )olu,ion o* aliza%in %e# an#

o,a))ium *e%%ic&ani#e ,o #i),ingui)h ca%bona,e

mine%al). Ca%bona,e an# cla& mine%al) o* 4'

)amle) >e%e anal&ze# b& %a& #i**%ac,ion u)ing

a 7hili) 7K3;10 %a& 7o>#e% Di**%ac,ome,e%

an# )uo%,e# b& )canning elec,%on mic%o)coe

E2 ob)e%"a,ion( aiming ,o cha%ac,e%ize

cemen, mo%holog&( o%e geome,%&( an# #ia

gene,ic %ela,ion)hi). The g%ain )ize an# %oc

como)i,ion) #e,%i,al an# au,higenic como

nen,)2 o* '' %e%e)en,a,i"e )amle) >e%e

e%*o%me# b& coun,ing B00 oin,) e% ,hin

)ec,ion. 7e,%oh&)ical %oe%,ie) >e%e #e,e%

mine# *%om 3B )amle) u)ing con"en,ional

helium o%o)ime,%& an# linenbe%gco%%ec,e#

ga) e%meame,%& b& !e)ea%ch n),i,u,e o*

inghai il*iel#( C/7C.

The ),able ca%bon an# o&gen i)o,oe) o*

ca%bona,e cemen,) o* 18 )amle) >e%e anal&ze#.

The anal&)i) >a) e%*o%me# on calci,e( #olomi,e(

*e%%o#olomi,e( an# )i#e%i,ecemen,e# )an#),one

)amle). The )amle) >e%e c%u)he# an# g%oun#

a) *ine a) o>#e% P100 me)h2 %io% ,o anal&)i).

Then( 100H ho)ho%ic aci# >a) #%oe# in,o

)amle o>#e% a, 'B QC *o% 36 hou%) ,o le, u%e

calci,e )amle) e,%ac, C' *%om ,he calci,e

*%ac,ion( ,hen a, B0 QC ,o ob,ain C' *%om

*e%%i*e%ou) calci,e( an# a, 100 QC ,o ob,ain C'

*%om ane%i,e. )o,oic como)i,ion >a) anal&ze#

on a Finnigan -T'B' ),able i)o,oe %a,io ma))

)ec,%ome,e% in ,he Geochemi),%& Dea%,men,(

,he Te), Cen,e% o* anzhou =%anch( Chine)e

-ca#em& o* cience). )o,oe "alue) >e%e %eo%,

e# in ),an#a%# #el,a no,a,ion a) e% mil R2

#i**e%ence *%om ,he 7D= ),an#a%#. !elica,e

mea)u%emen,) o* ,he in,e%nal labo%a,o%& ),an

#a%# ga"e a ,o,al anal&,ical %eci)ion o* S0.0'R

*o% bo,h ca%bon an# o&gen mea)u%emen,)

I10('0J. The e?ua,ion) o* C%aig >e%e u)e# ,o cal

cula,e ,he %ecii,a,ion ,eme%a,u%e o* )i#e%i,e(calci,e( an# ane%i,e I'1J.

RESULTS AND DISCUSSION

Petrographic Features and Mineralogical

Compositions

!e)e%"oi% )an#),one) in >ell 7M341' an# >ell

7M';'1 a%e mo),l& cla))i*ie# a) *ine ,o

me#iumg%aine# li,hic )uba%o)e( an# a *e> a)

)ubli,ha%eni,e. The a"e%age *%ame>o% como)i,ion o* ,he )an#),one) i) 69F1318 Figu%e 42.

Con,en, o* #e,%i,al ?ua%,z g%ain) i) highe% ,han

60H( li,hic g%ain) a%e le)) ,han '0H( an# *el#)a%

g%ain) a%e le)) ,han1;H Table 12. i,hic g%ain)

a%e #omina,e# b& "olcanic B19H2( mino% che%,(

?ua%,z )chi),( an# h&lli,e BH2. olcanic li,hic)

a%e )ligh,l& )e%ici,iza,e#. Diagene,ic comonen,)

a%e cha%ac,e%ize# b& mino% ?ua%,z o"e%g%o>,h

0.B1.1H2 an# ca%bona,e cemen, a"e%age BH2.

The #el,a *%on, )an#),one) a%e *ine ,o me#ium

g%aine# an# mo#e%a,el& )o%,e# I18J.

an#),one) ,aen *%om >ell 7M';11 a%e li,hic

)uba%o)e( >i,h a *e> a) )uba%o)e. The& a%e

*ine ,o me#iumg%aine# an# oo%l& ,o mo#e%

a,el& )o%,e#.

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B (

Ta9le 1 A,erage detrital composition and main diagenetic constituents in the deltaic front sandstones ;<

#etrital and #iagenetic Constituents@ell

P?%4:1:2

@ell

P?2D:2:1

@ell

P?2D:1:1Ea

@ell

P?2D:1:1E9

@ell

P?%%:1:1

amle 1B B 9 16 19

ua%,z 6B.9 ;1.; ;6 ;1.8 ;6.B*el#)a% 1'.B 1'.; 1'.6 1'.' 14.1

7lagiocla)e 1.1 1.4 1.4 '.; 1.1

olcanic !oc F%agmen,) 16 11 9.B 9.' 9.8

e,amo%hic !oc F%agmen,) B.6 4.; '.1 4.B 3.9

Chlo%i,e 0 0 0.; 0.8 0

aolini,e '.1 1.' 0.9 0.6B 1.8

lli,e 1.3 '.6 0.8B 0.B6 1.9

mec,i,e 0 0 ,%ace 0 0

i#e%i,e 0 0.4 ,%ace 0.' 0

Calci,e 4.6 1.B 9.6 4.B 9.B

Dolom-ne%i,e 1.4 1.' 1.3 0.4 1.B

n,e%g%anula% i#e%i,e 0.' 0.4 0.' 0.' 0.3

ua%,z "e%g%o>,h 0.B 1.1 0.B 0.9 0.8

7&%i,e ,%ace 0 ,%ace ,%ace 0

)igure 4 uart8:feldspar:lithic grain ternary plot

sho'ing the composition of the detrital grains of

the sandstones under -c.rideFs 1GB% classification

scheme 5227

The a"e%age *%ame>o% como)i,ion o* ,he

)an#),one) i) ;6F1311 in ,he ue% in,e%"al an#

;'F1'16 in ,he lo>e% in,e%"al. i,hic g%ain) a%e

mo%e abun#an, in ,he lo>e% in,e%"al an# a%e

mainl& "olcanic li,hic) B1BH2 Table 12. The

)amle) o* >ell 7M';11 a%e cha%ac,e%ize# b&

chlo%i,e cemen,) 0.;H2( ca%bona,e cemen,) '

1BH2( an# ?ua%,z o"e%g%o>,h 0.B0.9H2.

The )amle) o* >ell 7M3311 a%e cla))i*ie# a)

li,hic )uba%o)e( >i,h a *e> )uba%o)e( ha"ing

an a"e%age *%ame>o% como)i,ion o* ;;F149.

The )an#),one) a%e *ine ,o me#iumg%aine# an#

oo%l& ,o mo#e%a,el& )o%,e#. i,hic) a%e mainl&

"olcanic 9.8H2 an# ),%ongl& )e%ici,iza,e#.

Cha%ac,e%ize# #iagene,ic comonen,) a%e ca%

bona,e B1BH2 an# ?ua%,z o"e%g%o>,h 0.B1H2

Table 12.

Diagenetic Processes

Compaction and Pressure Dissolution

The)e )an#),one) a%e mo#e%a,el& ,o ),%ongl&

a**ec,e# b& comac,ion #u%ing bu%ial. Du%ing

comac,ion( mica la,e) >e%e mo#e%a,el& ,o

),%ongl& #e*o%me#. The ),%onge% comac,ion

occu%%e# in lo>e% )amle) o* >ell 7M3311.

olcanic %oc *%agmen,) >e%e ),%ongl& #e*o%me#

an# )?ueeze# in in,e%g%anula% o%e )ace)

8/11/2019 Jpst 2014 Vol. 4 No. 1





( D

be,>een ?ua%,z g%ain) Figu%e Ba2( a) in#ica,e# b&

,he )amle) *%om ,he #e,h lo>e% ,han 3400m.

G%ain con,ac,) a%e mainl& line an# conca"e

con"e con,ac,). ino% %igi# ?ua%,z g%ain) >e%e

%ea%%ange# an# occa)ionall& *%ac,u%e#. 7%e))u%e

#i))olu,ion a%,icula%l& occu%) bo,h along in,e%

g%anula% con,ac,) an# ),&loli,e) be,>een ?ua%,z

g%ain). 7%e))u%e #i))olu,ion no, onl& %e#uce)

%ima%& o%o)i,&( bu, al)o %o"i#e) ,he )olu,e

>hich >ill %ecii,a,e a%oun# ,he g%ain) a)

)econ#a%& o"e%g%o>,h an# >ill #e),%o& in,e%

g%anula% o%e).

)igure 6 ;a< @ell P?%4:1:2 ;H60< %%4G/B m =%28h

strongly compacted sandstones/ #uctile lithic grains

'ere strongly deformed and sIuee8ed into pore

spaces ;9< @ell P?%4:1:2 ;H100< %%1/G1 m =%28h

ferro:dolomite fills intragranular pores and replaces

Iuart8 grains ;c< @ell P?2D:1:1 ;H26< %2%G/B2 m

=%28h Iuart8 o,ergro'th 'ith dust lines 9et'een

them ;d< @ell P?2D:2:1 ;H60< %14%/D6 m =%28h

dissol,ed pores generated 9y dissolution of ,olcanic

de9ris/

Carbonate Cementation

Siderite

i#e%i,e i) ,&icall& le)) common in ,he)e

)an#),one)( bu, i, )igni*ican,l& )ho>) #iagene,ic

*ea,u%e). , occu%) commonl& a) )ca,,e%e#

c%&),al) an# conc%e,ion) in *ine ,o coa%)e

g%aine# )an#),one) Figu%e 6b2( >hich a%e oo%l&

)o%,e# an# mo#e%a,el& comac,e#. ca,,e%e#

c%&),al) a%e #e"eloe# a) cemen,) in *illing

in,e%g%anula% o%e) an# )econ#a%& o%e) *o%me#

b& ,he #i))olu,ion o* !F an# *el#)a%)(

gene%all& in#ica,ing ,ha, )i#e%i,e %e#a,e)

#i))olu,ion). -l)o( )i#e%i,e c%&),al) a%e a%,icu

la%l& embe##e# in ane%i,e conc%e,ion)( )ho>ing

,ha, )i#e%i,e %ecii,a,e# be*o%e ,he #e"elo

men, o* ane%i,e. i#e%i,e )ligh,l& %elace)

?ua%,z g%ain) in ,he )amle ,aen *%om ,he

#e,h o* 3'38.' m in >ell 7M';11 an# no

?ua%,z o"e%g%o>,h can be )een a%oun# ,he

?ua%,z g%ain) >%ae# b& )i#e%i,e cemen,).

)igure B S=- images of sandstones;a< @ell P?%4:1:

2 %%4/B% m =%28h 'ell P?2D:1:1 crystalli8ed

calcite cement ;9< @ell P?2D:1:1 2D1/12 m =%28h

siderite occurs as scattered crystals in intragranular

pores ;c< @ell P?%4:1:2 %%B/%2 m =%2

8hauthigenic Iuart8 cements that fill intragranular

space ;d< @ell P?2D:1:1 %221/D m =%28h authigenic

aolinite and partly filling pores/

i#e%i,e i) c%ea,e# in mino% amoun,) an# i)

al>a&) embe##e# in ane%i,e conc%e,ion). The

13

C "alue o* )i#e%i,e cemen, i) ;.'R an# ,he

18

"alue i) 11.4R Table '2. The %ela,i"el&

ligh, "alue in#ica,e) ,ha, ,he )ou%ce o* )i#e%i,e

cemen, >a) %ecii,a,e# *%om ,he a##i,ion o*

o%ganic ma,,e% #eca%bo&la,ion. , >a) %ecii

,a,e# %ela,i"el& la,e in #iagene,ic hi),o%& an#

%e#a,e# #i))olu,ion an# a%,) o* ane%i,e. The

%ecii,a,ion o* )i#e%i,e >a) a, a %e)e%"oi%

,eme%a,u%e o* 80 QC.

Calcite

Calci,e cemen,) ha"e a he,e%ogeneou)l& #i),%i

bu,ion an# ,en# ,o ha"e a ,>o),age #e"elo

men, in ,hi) ),u#&.

a b

c #

a b

#c

8/11/2019 Jpst 2014 Vol. 4 No. 1






(

Ta9le 2 3sotopic ratios of representati,e car9onate cements and temperatures calculated 9y Craig 5217

Sample o/ #epth ;m< Cement type K1%

C ;P#.< K1

;P#.< Temperature ;MC<

7M341'01C 3348.63 Calci,e ;.6 1'.' 86

7M341'0'C 3349.4 Calci,e 6.B 13.4 9B

7M341'03C 3349.86 Calci,e 6.1 1'.1 8B

7M341'04C 33B4.0' Calci,e 6.' 11.' ;9

7M341'0BC 33BB.4 Calci,e 6.8 1'.1 8B

7M341'06C 33BB.98 Calci,e 6 13 9'

7M341'13C 3381 Calci,e B.B 14.9 106

7M';'10'C 30'8.8 Calci,e 6.3 13.1 9'

7M';'103C 3034.B i#e%i,e ;.' 11.4 80

7M';1108C ';81.1' Calci,e B.4 13.B 9B

7M';1109C ';83.06 Calci,e B.9 1'.' 86

7M';1110C 3''1.; Calci,e 4.8 1'.B 88

7M';1116C 3'30.;B -ne%i,e 10.4 1'.3 86

7M';11'3C 3'41.3' Calci,e 8.9 13.; 9;

7M331108C 3433.3 Calci,e 4.B 9.1 64

7M331110C 3434.1 Calci,e B.4 11.9 84

7M331111C 343B.B -ne%i,e 6.' 8.9 63

7M331113C 343;.91 -ne%i,e ;.4 6.8 B0

Ea%l& cemen,a,ion) a%e %e%e)en,e# b& cemen,)

in )amle) a, ,he #e,h o* ';;1.68 m in >ell

7M';11 an# a, ,he #e,h o* 3433.3 m in >ell

7M3311. The )an#),one) a%e *ine ,o me#ium

g%aine# an# oo%l& )o%,e# >i,h a %ecalci,e ba)al

cemen,e#( >hich )ho>) a %ecomac,ional

cemen,a,ion. Calci,e occu%) a) ba)al cemen,)

>i,h a high con,en, o* 'B30H b& oin,coun,ing

#a,a in ,hin )ec,ion). The *o%ma,ion ,ime o* ,hi)

calci,e i) ea%lie% ,han ,he o,he% #iagene,ic

al,e%a,ion). F%ame>o% g%ain) >e%e >%ae# in

calci,e conc%e,ion) an# no ?ua%,z o"e%g%o>,h(

#i))olu,ion o* !F an# *el#)a%( an# chlo%i,e)

>e%e %e)en,.

a,e calci,e cemen,a,ion) a%e cha%ac,e%ize# a)

o%e*illing) an# conc%e,ion) in oo%l& )o%,e#(

*ine )an#),one) Figu%e 6a2. , )igni*ican,l& )ho>)

"a%ia,ion in #i),%ibu,ion *%om )amle ,o )amle

an# ha) a con,en, >hich %ange) *%om 'H ,o 14H

a"e%age B6H2. Calci,e cemen,) occu%) in

%elacing ?ua%,z g%ain) an# ?ua%,z o"e%g%o>,h

a%e %e)en,( )ho>ing ,ha, ,he& %ecii,a,e# a*,e%

,he #e"elomen, o* ?ua%,z o"e%g%o>,h).

The 13

C "alue) o* calci,e cemen,) %ange) *%om

4.B ,o 8.9R an# 18

*%om 9.1,o 14.9R Table

'2. Ea%l& calci,e cemen,) %ecii,a,e# ea%lie% ,en#

,o ha"e hea"ie% 13

C "alue). The C an# i)o,oic

"alue in#ica,e) ,ha, ,he )ou%ce i) mo),l& %ela,e#

,o ,he oi#a,ion o% #eca%bo&la,ion o* o%ganic

ma,,e% an# ha) a nega,i"e %ela,ion)hi >i,h

ino%ganic )ou%ce)( becau)e "a%iou) ),u#ie) ha"e

%eo%,e# ,ha, ,he 13

C "alue) o* ,he no%mal

ma%ine ca%bona,e %oc) an# cemen,) "a%&

be,>een 4R an# +4R 7D=2 I'0(''J. /o#i))olu,ion o* ca%bona,e *%agmen,) a) in,e%nal

)ou%ce o* calcium an# C' >a) ob)e%"e# in ,hi)

),u#& I'3J. Fo%me% ),u#ie) )ho> ,ha, >i,h

inc%ea)ing bu%ial #e,h( %e))u%e an# ,eme%a

,u%e inc%ea)e# ,o %omo,e ,he e"olu,ion o*

o%ganic ma,,e% in )ou%ce %oc) >hich >ill %elea)e

a%, o* ca%bon #ioi#e ga)e) >i,h ligh,e% ca%bon

i)o,oe I'0('4('BJ. The ligh,e% 13

C como)i,ion

>a) %elea)e#( ,hen #i))ol"e# in,o *lui# an#

con,%ibu,e# ,o ,he *o%ma,ion o* ca%bona,e

8/11/2019 Jpst 2014 Vol. 4 No. 1





( G

cemen,). -l)o( ha"ing ca%bon #ioi#e ga) been

inu, in,o *lui#( ,he en"i%onmen, >a) ,%an)

*o%me# in,o an aci#ic en"i%onmen,. Khen ,he

aci# en,e%e# ,he %e)e%"oi% )an#),one)( i, >ill

#i))ol"e ,he *el#)a%( li,hic g%ain)( an# ea%l&

ca%bona,e cemen,) ,o gene%a,e )econ#a%& o%e)

)ee Figu%e B#2 I'0J. Calci,e cemen, >a) %ecii

,a,e# a, ,eme%a,u%e) %anging *%om 64 QC ,o 106

QC calcula,e# b& ,he *o%mula li),e# b& Ahang I6J(

)ho>ing bo,h ea%l& an# la,e %ecii,a,ion) in

#iagene,ic hi),o%& I'6J. n #ee bu%ie#( )ou%ce

%oc) %eache# a high ma,u%i,& ),age >i,h high

,eme%a,u%e an# %e))u%e. The%e*o%e( h&#%o

ca%bon gene%a,ion *%om )ou%ce %oc) %eache# i,)

ea "olume. a%ge "olume o* h&#%oca%bon in*illing ,he )an#),one %e)e%"oi% cau)e# ,he *o%me%

aci#ic en"i%onmen, ,%an)*o%me# in,o an alaline

en"i%onmen, an# ligh,e%13

C#ele,e# ma,e%ial)

>e%e a##e# *o% calci,e %ecii,a,ion.

Anerite

-ne%i,e cemen, i) e,en)i"el& #e"eloe# in ,he

)an#),one) >i,h i,) con,en, le)) ,han calci,e. ,

commonl& occu%) a) o%e*illing) an# cemen,)

%elacing *%ame>o% g%ain). 7o%e*illing cemen,)

,&icall& occu% a*,e% e**ec,i"e comac,ion.

ua%,z g%ain)( ?ua%,z o"e%g%o>,h( an# li,hic

g%ain) a%e %elace# b& ane%i,e c%&),al) in ,he

)an#),one) Figu%e Bb2( in#ica,ing ,ha, ,hi)

ane%i,e )ho>) a cha%ac,e%i),ic o* la,e% #e"elo

men, ,han ?ua%,z o"e%g%o>,h). mall ane%i,e

c%&),al) al)o occu% a) cemen,) *illing in )econ#

a%& o%e) *o%me# b& ,he #i))olu,ion o* !F an#

*el#)a%)( cha%ac,e%izing ,ha, i, %ecii,a,e#

la,e% ,han ,he #i))olu,ion o* !F an# *el#)a%) in

,hi) ),u#&.

Th%ee ane%i,ecemen,e# )amle) >e%e ice#

,o anal&ze ca%bon an# o&gen i)o,oe como)i

,ion). The 13

C "alue) o* calci,e cemen,) %ange)

*%om 6.' ,o 10.4R an# 18

"a%ie) *%om 6.8 ,o

1'.3R Table '2. -ne%i,e >a) *o%me# a,

%e)e%"oi% ,eme%a,u%e) %anging *%om B0 QC ,o

86 QC calcula,e# b& ,he *o%mula li),e# b& Ahang

I6J( in#ica,ing bo,h ea%l& an# la,e %ecii,a,ion)

I'6J.

Quartz cements

The %ecii,a,ion o* ?ua%,z o"e%g%o>,h) occu%)

a*,e% e**ec,i"e bu%ial an# comac,ion. ua%,z

cemen,) in ,he )an#),one) occu% mainl& a)

?ua%,z o"e%g%o>,h) a%oun# ?ua%,z g%ain) an#

i)ola,e# a,che) an# a%e como)e# o* )mall

c%&),al) an# ,%ace amoun,) o* i)ola,e# ?ua%,z

c%&),al) >hich *ill in,e%g%anula% o%e )ace)

Figu%e 6c2 o% )econ#a%& #i))ol"e# o%e).

Di)con,inuou) o"e%g%o>,h i) common. , occu%)

on ?ua%,z )u%*ace >i,h a oo%l& #e*ine# boun#

a%&. ua%,z o"e%g%o>,h) ,en# ,o be much mo%e

abun#an, in ,he #eee% bu%ie# )an#),one) a,,he #e,h o* lo>e% ,han 3'00 m. 7a%,icula%l&(

,he amoun, o* ?ua%,z cemen, i) g%ea,l& limi,e#

in )amle) ,ha, ha"e a high con,en, o* #uc,ile

li,hic g%ain). Duc,ileli,hic con,en,) in >ell 7M34

1' an# ,he lo>e% )amle# in,e%"al o* >ell 7M';

11 a%e 613.B "ol.H an# B1; "ol.H %e)ec,i"el&(

>i,h ?ua%,z o"e%g%o>,h o* ,%ace ,o 1.4 "ol.H an#

1.B "ol.H %e)ec,i"el&. Duc,ileli,hic g%ain) a%e 3

B "ol.H an# much lo>e% in ,he )amle) o* >ell

7M3311( bu, ,he& ,en# ,o ha"e much highe%

?ua%,z o"e%g%o>,h o* '.3 ,o B "ol.H . Duc,ile

con,en,) aea% ,o con,%ol ,he amoun, o* ?ua%,z

cemen, becau)e #uc,ile li,hic g%ain) a%e #e*o%m

e# an# become clo)el& con,ac,e# >i,h ,he

)u%*ace o* %igi# g%ain) a) comac,ion inc%ea)e).

n )ome ca)e)( #uc,ile g%ain) a%e )?ueeze# in,o

in,e%g%anula% o%e )ace).

Gene%all&( ?ua%,z o"e%g%o>,h on #e,%i,al ?ua%,z

g%ain) i) inhibi,e# b& >ell #e"eloe# chlo%i,ecemen,) Figu%e ;a2. ua%,z o"e%g%o>,h) a%e

%e)en, >hen ?ua%,z g%ain) a%e no, coa,e# b&

chlo%i,e %im o% chlo%i,e %im i) ,hin o% #i)con,inuou).

Kell #e"eloe# chlo%i,e %im) la& ,he %ole o*

e**ec,i"e ba%%ie%) ,o inhibi, ?ua%,z o"e%g%o>,h I';J.

The )ou%ce) o* )ilica ma& ha"e been *%om ,h%ee

)ou%ce)( inclu#ing 12 ,he %e))u%e #i))olu,ion o*

#e,%i,al ?ua%,z along in,e%g%anula% con,ac,) an#

#i)c%e,e ),&loli,e) Figu%e Ba2( '2 ,he #i))olu,ion

8/11/2019 Jpst 2014 Vol. 4 No. 1






10 (

o% al,e%a,ion o* #e,%i,al )ilica,e)( mainl& "olcanic

%oc *%agmen,) Figu%e B#2( an# 32 ,he illi,iza

,ion o* #e,%i,al an# au,higenic aolini,e Figu%e

8a2.

)igure D ;a< @ell P?2D:1:1 ;H60< %4%2/14 m =%28h

chlorite rims and intergranular pores grain contact

and point:line contact ;9< @ell P?2D:2:1 ;H26<

%02/0 m =%28h intergranular and intragranular

pores rather open pore:structures for sandstonesof delta facies/

n common( ,he in,e%g%o>,h o* ?ua%,z i)

occu%%e# b& *ib%ou) illi,e( aolini,e( an# chlo%i,e

Figu%e 8c2. o%eo"e%( )iliceou) cemen,) )ou%ce#

*%om ,he #i))olu,ion o* *el#)a% a%e in#ica,e# b&

,he common occu%%ence o* in,e%g%o>,h o*

?ua%,z >i,h *ib%ou) illi,e( aolini,e( an# chlo%i,e

Figu%e 8c2.

Clay Minerals

Cla& mine%al) i#en,i*ie# in ,he )an#),one) o* ,he

),u#ie# a%ea inclu#e illi,e( aolini,e( chlo%i,e( an#

)mec,i,e. -) #e,e%mine# b& ,hin )ec,ion ob)e%

"a,ion)( E an# !D anal&)i)( lli,e an#

aolini,e a%e ,he mo), common cla& mine%al)

an# ,he& a%e %e)en, in almo), all ,he anal&ze#

)amle). The %e)ence o* chlo%i,e an# )mec,i,e

i) limi,e#.

aolini,e occu%) a) agg%ega,e) ),ace# b& )eu#o

heagonal c%&),al) %elacing *el#)a% g%ain). , *ill)

,he #i))ol"e# o%e) an# occu%) a#jacen, ,o

?ua%,z o"e%g%o>,h. aolini,e al)o occu%) a)

boole,) 1B Um ac%o))2 in *illing in,e%g%anula%

o%e )ace) an# a))ocia,e) >i,h ?ua%,z o"e%

g%o>,h Figu%e 6#2. -l,hough ,he%e i) no clea%

e"i#ence on ,he ma,e%ial )ou%ce *o% i,) %ecii,a

,ion( i, %e*e%en,iall& occu%) a))ocia,e# >i,h

?ua%,z o"e%g%o>,h. n )ome ca)e)( aolini,e

occu%) a) i)ola,e# an# #i)o%#e%e# c%&),al) B Um2

engul*e# b& illi,e c%&),al). aolini,e ha) a highl&

i%%egula% #i),%ibu,ion an# i,) amoun, "a%ie) *%om

)amle ,o )amle. , como)e) u ,o abou, 4H

o* ,he %oc) an# occuie) u ,o abou, 4BH o*,he cla& mine%al).

)igure S=- images of sandstones;a< @ell P?2D:2:

1 %B%0/26 m =%28h fi9rous illite crystals in deep

9uried sandstones ;9< @ell P?2D:1:1 %244/D m

=%28h fine:crystalline chlorite rims co,ering detrital

Iuart8 grains ;c< @ell P?2D:1:1 %2%G/B2 m =%28h

Iuart8 o,ergro'th and chlorite coat co,ering Iuart8

grains ;d< @ell P?%%:1:1 %2GG/6 m =%28h

dissolution of feldspar generates a9undant second:

ary pores/

lli,e i) *oun# mo),l& in o%e )ace) an# a%,l&

>i,hin ,he ma,%i. , i) %e%e)en,e# b& ,h%ee

#i**e%en, ,e,u%e ,&e)( namel& 12 hai%lie(

%a#icall& #i)o)e# c%&),al) Figu%e 8a2 >hich occu%

a) o%e*illing an# o%elining cemen,N '2 *ib%ou)

c%&),al)N an# 32 memb%anou) ),%uc,u%e)( >hich

occu% a) o%e*illing an# o%elining cemen,).

lli,e *o%m) u ,o abou, BH o* ,he %oc) an#*o%m) u ,o B0H o* ,he cla& mine%al). ou%ce) o*

illi,e cemen, a%e mo),l& *%om ,he al,e%a,ion o*

*el#)a% an# !F an# )mec,i,e).

Chlo%i,e cemen, i) onl& *oun# in ,he )amle) o*

>ell 7M';11 an# ,he amoun, "a%ie) *o%m 0.B

'H. - %ela,ion)hi be,>een chlo%i,e cemen, an#

highe% o%o)i,& in ,he )amle) i) ob)e%"e# in ,hi)

),u#&. Chlo%i,e i) %e)en, in ,h%ee *o%m)( namel&

o%e*illing an# o%elining cemen,) PB Um2(

8/11/2019 Jpst 2014 Vol. 4 No. 1





( 11

c%&),al agg%ega,e) *illing >i,hin ,he o%e) an#

g%o>ing on ,he )u%*ace o* #e,%i,al g%ain) Figu%e

8b an# 8c( Figu%e ;a2( an# chlo%i,e coa,ing)

>hich in#ica,e a %ecomac,ional %ecii,a,ion

an# a%e #e*o%me# be,>een a#jacen, %igi# g%ain)

a) comac,ion inc%ea)e). , i) ,he mo), imo%

,an, ,&e o* cla& mine%al). ince o,he% cemen,)

a%e inhibi,e# b& chlo%i,e cemen,)( #e,%i,al g%ain)

coa,e# b& chlo%i,e a%e clean. i,,le o% no ?ua%,z

o"e%g%o>,h) a%e #e"eloe# in )amle) >hen

#e,%i,al g%ain) a%e coa,e#N i, i) onl& #e"eloe# in

)ace) >he%e chlo%i,e %im) a%e ,hin o% #i)con,in

uou) a) )ho>n in E image). !F an# *el#)a%

g%ain) a%e a%,iall& ,o comle,el& #i))ol"e# in

,he )amle) >i,hou, chlo%i,e coa,ing). ence,he #e"elomen, o* chlo%i,e %im) a%oun# #e,%i,al

g%ain) aea%) ,o ha"e hele# ,he %e"en,ion o*

,he #i))olu,ion o* !F an# *el#)a% g%ain) b&

o%e >a,e%. The #e"elomen, o* chlo%i,e %im)

ha) al)o hele# ,he %e)e%"a,ion o* o%o)i,& b&

enhancing ,he mechanical ),%eng,h o* ,he

#e,%i,al g%ain) again), mechanical comac,ion

an# %e))u%e #i))olu,ion. -l,hough no #i%ec,

e"i#ence *o% con*i%ming ,he )ou%ce o* chlo%i,e

cemen, i) )ho>n( ,he #i))olu,ion o* !F mu),

%o"i#e abun#an, Fe'+

an# g'+

in,o o%e

>a,e%) ,o hel ,he ,%an)*o%ma,ion o* chlo%i,e

cemen,).

mec,i,e cemen,) a%e mino% in ,he ),u#ie#

)an#),one) acco%#ing ,o ,he E e"i#ence an#

!D #a,a an# a%e mo),l& #e"eloe# a, ,he

#e,h) lo>e% ,han 3000 m. ,) con,en, i) in ,he

o%#e% o* ,%ace) in ,he mo), ,e),e# )amle) an# i)

lo>e% ,han 1H in ,he )amle) ,aen *%om ,he#e,h) o* ';6B m an# ';68 m. The cu%%en, >o%

)ho>) ,ha, )mec,i,e *o%m) ea%l& in eo#iagene)i)

an# ee%ience) illi,iza,ion o% #i))olu,ion. The

illi,iza,ion o* )mec,i,e cemen,) occu%) >hen -l3+

an# + a%e a##e# in,o o%e *lui#). Thi) %eac,ion

al)o %elea)e) abun#an, i4+

a) one o))ible

)ou%ce o* ?ua%,z cemen,.

Diagenetic Sequence

Diagene,ic %oce)) i) clo)el& %ela,e# ,o o%o)i,&

e"olu,ion( bu, ,he ,iming o* #i**e%en, %oce))e)

an# ,hei% e**ec,) on o%o)i,& "a%& g%ea,l& #u%ing

,he bu%ial hi),o%& o* %e)e%"oi% )an#),one).

The%e*o%e( #e,aile# un#e%),an#ing o* #iagene,ic

)e?uence i) hel*ul *o% *in#ing ,he majo%

con,%olling *ac,o%) o* %e)e%"oi% ?uali,& an#

%e#ic,ing %e)e%"oi% ?uali,ie). =a)e# on ,he

abo"e ob)e%"a,ion) o* #iagene,ic cha%ac,e%i),ic)(

,he )e?uence o* au,higenic mine%al)( *ab%ic

*ea,u%e) con,ac, o* #e,%i,al g%ain) an# o%e

,&e)( e,c2( e"olu,ion( coei),ing %ela,ion)hi o*au,higenic mine%al)( h&#%oca%bon mig%a,ion an#

emlacemen,( ,&omo%hic mine%al) %ecii

,a,e# in aci# an# alaline en"i%onmen,( ,he

#iagene,ic en"i%onmen,( #iagene,ic ha)e)( an#

#iagene,ic )e?uence o* ,he %e)e%"oi% )an#),one)

ha"e been con),%uc,e#.

an#),one) bu%ie# a, ,he #e,h o* le)) ,han

3000 m in ,he Ahuhai *o%ma,ion a%e mainl& in

,he -1 ),age o* me)o#iagene)i)( >hile ,ho)e

bu%ie# a, ,he #e,h o* g%ea,e% ,han 3000 m a%e

in ,he -' ),age o* me)o#iagene)i). Diagene,ic

en"i%onmen, in ,he *i%), ),age i) ),%ongl& aci#ic

an# g%a#uall& )>i,che# ,o >eal& aci#ic an#

*inall& >eal& alaline in ,he la,e ),age. Diagen

e,ic )e?uence in ,he %e)e%"oi% )an#),one) i)

)chema,icall& illu),%a,e# in Figu%e 9. n )umma%&(

,he #iagene,ic g%a#a,ion o* #el,aic )an#),one) can

gene%all& be a%%ange# a):

Comac,ionV ea%l& cla& coaWng) V ea%l&

ca%bona,e cemen,) V o%ganic aci#) in"a#ing V

,he #i))olu,ion o* "olcanic %oc *%agmen,) an#

*el#)a%) V aolini,e an# ?ua%,z o"e%g%o>,h V

me,aha)e ca%bona,e cemen,) V h&#%oca%bon

a,e emlacemen, V ,he #i)lacemen, o* ?ua%,z

g%ain) b& la,e ca%bona,e cemen,).

8/11/2019 Jpst 2014 Vol. 4 No. 1






12 (

)igure G Paragenetic seIuence for the main diagenetic processes occurring in the sandstones as interpreted

from petrographic relationships #= #iagenetic temperature Tem Temperature Strata temperature 'as

modified after Pang et al/ 57/

echanical comac,ion an# #i))olu,ion a%e ,he

mo), imo%,an, #iagene,ic *ea,u%e) in ,he

#el,aic )an#),one) o* Ahuhai *o%ma,ion. The)an#),one) ee%ience ,&icall& me#ium me

chanical comac,ion ,h%ough bu%ial hi),o%& an#

mul,iha)e #i))olu,ion b& aci# *lui# #i)cha%ge#

b& mul,ile )e, o* )ou%ce %oc). The -1 ),age o*

me)o#iagene)i) )eci*icall& ha) a ),%ong aci#

en"i%onmen, >i,h abun#an, o%ganic aci# in o%e

>a,e%). Gene%all&( in ,hi) ),age( ,he comlica,e#

*lui#%oc in,e%ac,ion i) >i#el& #e"eloe#. -bun

#an, )econ#a%& o%e) a%e gene%a,e# b& ,he

),%ong #i))olu,ion o* !F an# *el#)a%)( an# ,he

*o%me# )econ#a%& o%e zone im%o"e) ,he

connec,i"i,& o* o%e) in ,hi) ),age.

Petrophysical Properties

Pore Types

7o%e ,&e) in ,he )an#),one) o* Ahuhai *o%ma

,ion inclu#e %e)i#ual in,e%g%anula% o%e( in,e%

g%anula% #i))olu,ion o%e( in,%ag%anula% #i)

)ol"e# o%e( in,e%c%&),alline o%e *%ac,u%e( an#

mino% mic%oo%e) in in,e%),i,ial ma,e%ial) Table

32. The mo), )igni*ican, o%e ,&e) a%e in,e%g%anula% o%e( in,e%g%anula% #i))olu,ion o%e(

an# in,%ag%anula% #i))olu,ion o%e. The a"e%age

"olume o* in,e%g%anula% o%e "a%ie) *%om 14

"ol.H ,o 4' "ol.H a"e%age '3 "ol.H2 o* ,he ,o,al

o%o)i,&. The )econ#a%& o%e) inclu#ing in,e%

g%anula% #i))olu,ion o%e an# in,%ag%anula%

o%e2 %ange) *%om BB "ol.H ,o 84 "ol.H a"e%age

;B "ol.H2 o* ,he ,o,al o%o)i,&. ic%oo%e(

in,e%c%&),alline o%e( an# *%ac,u%e o%e a%e

"olume,%icall& limi,e# ,o a "olume o* 13H o* ,he

,o,al o%o)i,&.

Porosity and Permeability

The %e)e%"oi% ?uali,& anal&)i) o* )an#),one)

ob,aine# *%om ,he *ou% >ell) )ho>) ,ha,

o%o)i,& %ange) *%om '.3H'B.4H a"e%age

13.9H2 an# e%meabili,& "a%ie) *%om 0.0;L103

m# ,o 1310L103

m# a"e%age 133.9L103

m#2.

8/11/2019 Jpst 2014 Vol. 4 No. 1





( 1%

Ta9le % A,erage ,alues of sandstone pore types Pore data are from thin:section data9ase/

@ell

Pore types

P?%4:1:2 P?2D:2:1 P?%%:1:1 P?2D:1:1Ea P?2D:1:1E9

n,e%g%anula% o%e 14H 1BH 'BH 19H 4'H

n,e%g%anula% Di))olu,ion o%e ;3H 46H 64H 34H 48H

n,%ag%anula% 7o%e 11H 3;H 9H 4BH 9H

n,e%c%&),alline X*%ac,u%eXmic%oo%e 'H 3H 'H 'H 1H

)igure 10 The relationship 9et'een measured porosity and permea9ility for the samples from Panyu lo':

uplift

F%om ,he ,o,al o%o)i,& an# e%meabili,& #a,a

*%om Ahuhai *o%ma,ion( 16.BH o* )an#),one)

ha"e a o%o)i,& )malle% ,han 10H( 31.BH be,

>een 10H an# 1BH( 4B.'H be,>een 1BH an#

'0H( an# 6.8H be,>een '0H an# 'BH. The "alue

o* e%meabili,& lo>e% ,han 10L103

Um' %eache)

4'.4HN '3.3H o* e%meabili,& "alue) lie be,>een10L10

3 Um

' an# 100L10

3Um

'N 19.'H o* ,he

"alue) a%e be,>een 100L103

Um' an# 300L10

3

Um' an# 1B.1H a%e g%ea,e% ,han 300L10

3Um

'

Figu%e 102.

Porosity Evolution

=a)e# on ,he e,%og%ahic ob)e%"a,ion)( #iagen

e)i) )eci*icall& con,%ol) %e)e%"oi% ?uali,&(

inclu#ing mechanical comac,ion( #i))olu,ion(

cemen,a,ion( au,higenic mine%al *illing( e,c.

Gene%all&( mechanical comac,ion occu%)

,h%ough ,he en,i%e bu%ial hi),o%& o* )an#),one)

an# la&) a majo% %ole in o%o)i,& %e#uc,ion.

Di))olu,ion c%ea,e) )econ#a%& o%o)i,& an#

e%meabili,&. , g%ea,l& im%o"e) )an#),one %e

)e%"oi% ?uali,& in ,he ),u#ie# a%ea. -##i,ionall&(

cemen,a,ion ca%bona,e an# ?ua%,z2 cau)e# ,he

%og%e))i"e lo)) o* o%o)i,& an# e%meabili,&

#u%ing bu%ial. Con)i#e%ing ,he #i**e%en, e**ec,)

o* majo% #iagene,ic %oce))e) on %e)e%"oi%

?uali,&( o%o)i,& e"olu,ion can be #i"i#e# in,o

,h%ee ),age) a) *ollo>) Figu%e 92:

12 - ),age o* eo#iagene)i)N ,he bu%ial #e,h o*

)an#),one) i) lo>e% ,han 1B00m an# i) mainl& in

a >ea alaline #iagene,ic en"i%onmen,). n ,hi)

),age( a**ec,e# b& o"e%l&ing ),a,ic %e))u%e(

o%o)i,& i) )ha%l& %e#uce# becau)e o* ,he

7e%meabili,& L103 Ym'2

8/11/2019 Jpst 2014 Vol. 4 No. 1






14 (

%ea%%angemen, o* #e,%i,al g%ain) an# ,he #i)

cha%ge o* o%e >a,e%). De,%i,al g%ain) become

oin, con,ac,. 7o%e ,&e i) mainl& %ima%& o%e.

n >eal& alaline #iagene,ic en"i%onmen,)(

ea%l& calci,e an# ane%i,e begin ,o %ecii,a,ean# *ill in,e%g%anula% o%e). The %e%e)en,a,i"e

)amle i) )amle *%om ,he #e,h o* ';;1.68 m

an# 3433.3 m %e)ec,i"el& *%om >ell 7M';11

an# 7M341'. The con,en,) o* ca%bona,e

cemen,) a%e '030 "ol.H >i,h a %ecemen,e#

o%o)i,& o* 404BH un#e% ,hin)ec,ion. Ea%l&

chlo%i,e) begin ,o %ecii,a,e >hen #iagene,ic

,eme%a,u%e i) le)) ,han B0 QC an# be*o%e e**ec,

,i"e comac,ion ),a%,). n,e%g%anula% o%e) a%e

e**ec,i"el& %e)e%"e# in )an#),one) >i,h >ell

#e"eloe# chlo%i,e coa,ing). Gene%all&( ea%l&

mechanical comac,ion %e#uce) o%o)i,& b& B

10H an# ea%l& ca%bona,e cemen,) #ec%ea)e)

o%o)i,& b& B10H.

'2 = ),age o* eo#iagene)i)Zan ea%l& -1 ),age o*

me)o#iagene)i)N ,he bu%ial #e,h o* )an#),one)

%ange) *%om 1B00 ,o 'B00 m. De,%i,al g%ain) a%e

mainl& oin, an# oin,line con,ac,. 7o%e) a, ,hi)

),age a%e mainl& %ima%& o%e). Di))olu,iono%e) begin ,o #e"elo >i,h #iagene,ic en"i%on

men, g%a#uall& change# *%om a >eal& alaline

,o a >eal& aci#ic en"i%onmen,. echanical

comac,ion i) enhance# b& o"e%bu%#en )e#i

men,) an# g%ea,l& %e#uce) o%o)i,& ,h%ough

bu%ial. Ca%bona,e cemen,) con,inue ,o %ecii

,a,e an# *ill in,e%g%anula% o%e) an# e**ec,i"el&

%e#uce in,e%g%anula% o%o)i,&. -, ,hi) ),age( cla&

mine%al) an# ?ua%,z o"e%g%o>,h begin ,o

%ecii,a,e an# a%e >i#el& #e"eloe# in ,he

),u#ie# a%ea( bu, >i,h a limi,e# e**ec, on o%o

)i,& %e#uc,ion. Kea #i))olu,ion ,&icall& begin)

,o occu% a) aci# *lui# en,e%e# ,he o%e >a,e%).

Gene%all&( mechanical comac,ion %e#uce) o%

o)i,& b& B1BH an# ca%bona,e cemen,) #e

c%ea)e) o%o)i,& b& B'BH.

32 -1 ),age-' ),age o* me)o#iagene)i)N ,he

bu%ial #e,h o* )an#),one) %ange) *%om 'B00 ,o

3B00 m. De,%i,al g%ain) a%e oin,line an# line

con,ac,. Diagene,ic en"i%onmen,) ha"e )>i,che#

*%om >eal& aci#ic ,o ),%ongl& aci#ic. -, ,hi)

),age( ,he mo), cha%ac,e%izing *ea,u%e i) ,ha,

o%ganic aci# #i)cha%ge# *%om lo> ma,u%e ,o

ma,u%e o%ganic ma,,e% i) a##e# in,o o%e>a,e%). The& ),%ongl& #i))ol"e !F( *el#)a%( an#

ea%l& ca%bona,e cemen,). Gene%all&( mechanical

comac,ion %e#uce) o%o)i,& b& B1BH an#

cemen,a,ion b& '10H. Khile( ),%ong #i))olu,ion

g%ea,l& im%o"e) an# inc%ea)e) o%o)i,& b& B

1'H. - )econ#a%& o%o)i,& zone i) #e"eloe# in

,he #e,h) in,e%"al be,>een ';B0 an# 3B00 m.

Thi) i) ,he %ea)on >h& %e)e%"oi% ?uali,& in

)an#),one) o* Ahuhai *o%ma,ion i) g%ea,l&

im%o"e#.

Major Factors Controlling Reservoir

Quality

Compaction and Porosity

echanical comac,ion i) )imle bu, la&) a

majo% %ole in %e#ucing o%o)i,& Figu%e 112.

b"iou) e"i#ence o* mechanical comac,ion in

%e#ucing o%o)i,& i) )ho>n. Co%%e)on#ingl&(

o%o)i,& i) lo), #u%ing ,he %oce))e) o* in,e%

g%anula% %ea%%angemen,( #e*o%ma,ion o* #uc,ile

g%ain)( e,c. Thin )ec,ion ),u#ie) )ho> ,ha, g%ain

con,ac, e"ol"e) *%om )ea%a,ion ,o oin, ,o

oin,line an# ,o line con,ac, becau)e o* ),%ong

comac,ion *%om )hallo> ,o #ee bu%ial. Thi)

cha%ac,e%i),ic al)o in#ica,e) ,he %ela,ion)hi o*

o%o)i,& >i,h bu%ial #e,h. Thu) o%o)i,& %e

#uce# b& comac,ion can be #i"i#e# in,o ,>o

),age)( namel& eo#iagene)i) P'000 m2 an#

me)o#iagene)i) '0003B00 m2. -"e%age %i

ma%& o%o)i,& in #el,aic )an#),one) >a)

a))ume# ,o be 40H imme#ia,el& a*,e% #eo)i

,ion I'8J. , ,en#e# ,o #ec%ea)e in,en)i"el& >i,h

inc%ea)ing ,he #e,h o* bu%ial an# %ela,i"el&

#ec%ea)e# *%om 40H ,o le)) ,han 'BH in

eo#iagene)i). The %a,e o* %e#uc,ion in o%o)i,&

b& comac,ion >a) )lo>e% in me)o#iagene)i)

,han in eo#iagene)i) an# became le)) ,han '0H.

8/11/2019 Jpst 2014 Vol. 4 No. 1





( 16

)igure 11 Plot of cement ,olume percent ,s/ intergranular ,olume percent of Panyu lo':uplift sandstones

;cf/ >ousenecht 527</ Compaction and cementation had a similar importance in the destruction of porosity

in the deltaic sandstones of Panyu lo':uplift/

Dissolution and Porosity

Di))olu,ion i) ,he main *ac,o% gene%a,ing

)econ#a%& o%o)i,&( >hich la&) a e& %ole in

o%o)i,& e"olu,ion. Thin )ec,ion an# E

ob)e%"a,ion) )ho> ,ha, ,he con,en, o* un),able

comonen,) i) "olume,%icall& high an# can be

cla))i*ie# in,o ,h%ee ca,ego%ie) inclu#ing !F B

30H2( *el#)a% 'BH2( an# ea%l& ca%bona,e

cemen,) B30H2. n ,he ),u#ie# a%ea( #i))olu,ion begin) in ,he = ),age o* eo#iagene)i)(

an# un),able con),i,uen,) a%e #i))ol"e# >hen

o%ganic aci# en,e%) in,o o%e >a,e%. n ,he -1

),age o* me)o#iagene)i)( abun#an, o%ganic aci#

i) #i)cha%ge# b& ,he e"olu,ion o* )ou%ce %oc

an# i) a##e# in,o o%e >a,e%). The un),able

con),i,uen,) a%e ),%ongl& #i))ol"e# in ,he aci#

en"i%onmen,. The %ela,ion)hi be,>een o%o)i,&

an# #e,h )ho>) ,ha, a )econ#a%& o%o)i,& zone

i) #e"eloe# in ,he #e,h in,e%"al be,>een ';B0

an# 3B00 m. n ,hi) in,e%"al( in,e%g%anula%

#i))olu,ion o%e an# in,%ag%anula% #i))olu,ion

o%e a%e abun#an,l& gene%a,e#. econ#a%&

o%o)i,& gene%a,e# b& #i))olu,ion ma& %each B

1BH acco%#ing ,o ,hin )ec,ion #a,aba)e.

Carbonate Cementation and Porosity

Ca%bona,e cemen, i) a main *ac,o% in con,%olling

)an#),one %e)e%"oi% %oe%,ie) Figu%e 112 an#

ma& ha"e a ),%ong in*luence on *lui# *lo>

I''('9J. Ca%bona,e cemen,) a%e >i#el& #e"el

oe# in )an#),one) *%om ,he *ou% >ell) Figu%e

1'2. The e**ec,) o* ca%bona,e cemen,) on

o%o)i,& a%e e"i#en,l& ob)e%"e# b& ,he %ela,ion

be,>een ,he amoun,) o* ,he cemen, an# ,he

mea)u%e# o%o)i,& an# e%meabili,& Figu%e 132.

Khen ,he con,en, o* ca%bona,e cemen, i) highe%

,han 1BH( ,he o%o)i,& i) no%mall& lo>e% ,han

10H.

8/11/2019 Jpst 2014 Vol. 4 No. 1






1B (

)igure 12 Sampled inter,als from 'ell P?2D:2:1 P?2D:1:1 P?%4:1:2 and P?%%:1:1 Lithology and macro:

sedimentary facies are interpreted 9ased on log response and core samples taen from the inter,als/

n ,he o,he% han#( >hen i,) con,en, i) le)) ,han10H( ,he o%o)i,& ma& %each 'BH. -n in"e%)e

%ela,ion)hi i) al)o )een be,>een ca%bona,e

con,en, an# e%meabili,& Figu%e 13b2. Ca%bon

a,e cemen,) occu% in ,he ,hicne)) %ange o* 0.B

m ,o lo>e% ,han 4 m an# ac, a) a main o%o)i,&

%e#ucing *ac,o% coma%e# >i,h ,he o,he%

cemen,) Figu%e 1'2. Fineg%aine# )an#),one)

a%e gene%all& mo%e *a"o%able *o% ,he #e"elo

men, o* ca%bona,e cemen,) ,han ,he coa%)e

g%aine# )an#),one). Thin )an#),one) ha"ehighe% ca%bona,e cemen,) ,han ,hic )an#

),one). Fu%,he%( ,hic )an#),one) ,en# ,o ha"e

ca%bona,e cemen,) in ,he ue% an# lo>e%

%ange) o* ,he in,e%"al). 7oo% ?uali,& i) ,&icall&

%ela,e# ,o ca%bona,e cemen,) in ,he ),u#ie#

)an#),one) *%om ,he ,>o >ell)( >hich a%e

#e"eloe# a, ,he #e,h) be,>een ';69 ,o ';;1

m an# ';;B ,o ';80.B m. o#e%a,el& ,o ),%ongl&

comac,e# )amle) ,aen *%om ,he #e,h o*

';69.B8 m *%om ,he *i%), in,e%"al a%e mo),l&

cha%ac,e%ize# b& ,he high amoun, o* ane%i,e

an# 0.'H o* )i#e%i,e cemen,. -ne%i,e an#

)i#e%i,e cemen,) *ill in in,e%g%anula% o%e) an#

#i))ol"e# o%e) an# g%ea,l& #e),%o& o%o)i,&.

The lo>e% a%, ';;B ,o ';80.B m2 i) mo),l&

cha%ac,e%ize# b& ,he high con,en, o* calci,e

cemen,( g%ea,l& #e),%o&ing o%o)i,&. Thi) e"i

#ence ei),) in )amle) lie ,he )amle o* ,he

#e,h o* ';;9 m >i,h i,) con,en, o* 30H "e%)u)

,he o%o)i,& o* 9H. an#),one) *%om ,he)amle# in,e%"al in >ell 7M3311 a%e

cha%ac,e%ize# b& lo> o%o)i,& an# lo> e%mea

bili,& mean "alue o* o%o)i,& i) 1'H an# ,he

e%meabili,& i) 33 Um'2.

)igure 1% +eser,oir Iuality data from the

sandstones in Panyu lo':uplift ;a< porosity ,s/

car9onate content ;9< permea9ility ,s/ car9onate

content/

an#),one) *%om ,he #e,h o* lo>e% ,han 3434

0

5

10

15

20

25

30

35

40

45

0 5 10 15 20 25 30 35 40Porosity(%)

C a r b o n

a t e c o n t e n t ( % )

0

2

46

8

10

12

14

16

0 100 200 300 400Permeability（10

-3µm

2）

C a r b o n a t e c o n t e n t ( % )

a

9

7o%o)i,& H2

7e%meabili,& L103 Ym

'2

8/11/2019 Jpst 2014 Vol. 4 No. 1





( 1D

m a%e mo#e%a,el& ,o ),%ongl& ca%bona,e

cemen,e# a%,icula%l& calci,e an# ane%i,e

cemen,2. -ne%i,e cemen,) a%e highl& #e"eloe#

in ,he )an#),one) loca,e# a, ,he #e,h) mo%e

,han 3434 m an# mo#e%a,el& #i)lace #e,%i,al

g%ain). =o,h o* ,hem la& an imo%,an, %ole in

%e#ucing o%o)i,& in ,he ),u#ie# in,e%"al).

CONCLUSIONS

1 The )hel*ma%gin #el,aic )an#),one %e)e%"oi% o*

Ahuhai *o%ma,ion *%om 7an&u lo>uli*, i) *ine

,o me#iumg%aine# li,hic )uba%o)e( )ub

li,ha%eni,e( an# )uba%o)e. ajo% #iagene)i)

conclu#e) comac,ion( #i))olu,ion !F(

*el#)a%( an# ca%bona,e cemen,)2( cemen,a,ionca%bona,e an# ?ua%,z o"e%g%o>,h2( an#

au,higenic mine%al *illing) aolini,e( chlo%i,e(

illi,e( an# )mec,i,e2.

' Comac,ion occu%%e# ,h%ough all ,he en,i%e

bu%ial hi),o%& an# la&e# a majo% %ole in

o%o)i,& %e#uc,ion. The e**ec, o* comac,ion

on o%o)i,& %e#uc,ion can be #i"i#e# in,o ,>o

),age)( namel& eo#iagene)i) an# me)o

#iagene)i). n eo#iagene)i)( o%o)i,& >a)

)ha%l& %e#uce# becau)e o* ,he %ea%%angemen,

o* #e,%i,al g%ain) an# #i)cha%ge o* o%e >a,e%)

a) comac,ion inc%ea)e#. n me)o#iagene)i)(

o%o)i,& >a) ),abl& %e#uce# b& comac,ion bu,

much )lo>e% ,han ,he *i%), ),age.

3 Di))olu,ion >a) ,he e& *ac,o% ,ha, im%o"e#

,he %e)e%"oi% ?uali,& o* ,he )hel*ma%gin

)an#),one). Di))olu,ion began in ,he = ),age

o* eo#iagene)i) an# con,inue# ,o #e"elo in

,he -' ),age o* me)o#iagene)i). -ci#ic o%e*lui#) #i))ol"e# !F( *el#)a%( an# ca%bona,e

cemen,) an# gene%a,e# )econ#a%& o%e).

n,e%g%anula% #i))olu,ion o%e an# in,%a

g%anula% #i))olu,ion o%e >e%e ,he main o%e

,&e) in ,he ),u#ie# a%ea. ,%ong an# e,en

)i"el& #i))olu,ion in Ahuhai *o%ma,ion c%ea,e#

a )econ#a%& o%o)i,& zone in ,he #e,h

in,e%"al be,>een ';B0 an# 3B00 m. , g%ea,l&

im%o"e# %e)e%"oi% ?uali,& in ,he ),u#ie#

a%ea.

4 Ca%bona,e cemen,) calci,e( )i#e%i,e( an#

ane%i,e2 >e%e *o%me# ea%l& in ,he - ),age o*

eo#iagene)i) an# con,inue# ,o ,he -' ),age

o* me)o#iagene)i). The& la&e# an imo%

,an, %ole in ,he %e)e%"oi% ?uali,& e"olu,ion o*

)hel*ma%gin )an#),one). n eo#iagene)i)(

ca%bona,e cemen,) >e%e mainl& *o%me#

>hich e**ec,i"el& %e"en,e# comac,ion an#

,he occuie# o%e )ace) ,%an)*o%me# in,o

#i))olu,ion o%e )ace) >hen ,he& >e%e

#i))ol"e# la,e% in me)o#iagene)i). o%e

o"e%( ca%bona,e cemen,) *o%me# in me)o

#iagene)i)( e)eciall& in ,he -' ),age( *ille# in

in,e%g%anula% o%e) an# #i))olu,ion o%e) o%

#i)lace# #e,%i,al g%ain) an# g%ea,l&#e),%o&e# %e)e%"oi% ?uali,&. Ca%bona,e

cemen,) ha# an in"e%)e %ela,ion)hi >i,h

%e)e%"oi% ?uali,&. Gene%all&( o%o)i,& an#

e%meabili,& >e%e highe% *o% ,he )amle)

con,aining a )malle% amoun, o* ca%bona,e

cemen,).

ACKNOWLEDGMENTS

Thi) ),u#& >a) join,l& *un#e# b& ,he China

/a,ional cienceTechnolog& 7%ojec, '011

A0B0'B0062 an# China 9;3 e& Foun#a,ion

!e)ea%ch De"elomen, 7%ojec, '009C='194002.

Ke al)o e%e)) ou% g%a,i,u#e ,o hu,ong i

*%om The e& abo%a,o%& o* 7e,%oleum !e

)ou%ce) !e)ea%ch( n),i,u,e o* Geolog& an# Geo

h&)ic)( an# Chine)e -ca#em& o* cience)N

C/C !e)ea%ch Cen,e% %o"i#e# all ,he ),u#ie#

)amle).

NOMENCLATURE

= =ai&un )ag

C/C China /a,ional **)ho%e il

Co%o%a,ion

C/7C China /a,ional 7e,%oleum

Co%o%a,ion

C<= Cen,%al uli*, bel,

a illion &ea%)

/<= /o%,he%n uli*, bel,

7D= 7ee#ee =elemni,e

8/11/2019 Jpst 2014 Vol. 4 No. 1






1 (

7!= 7ea%l !i"e% ou,h =a)in

D/= iong#ongnan ba)in

E canning elec,%on mic%o)coe

<= ou,he%n uli*, bel,

!F olcanic %oc *%agmen,)!D %a& #i**%ac,ion

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8/11/2019 Jpst 2014 Vol. 4 No. 1




Saeid Ahmadjo


Tel: +98 21 4866 2475

Fa:+98 21 4866 2475

Article history

!ecei"ed: #a$ 17% 2&1'

!ecei"ed i( re"ised )orm: *a(ar$ &8% 2&14

Accep,ed: *a(ar$ 18% 2&14

A"aila-le o(li(e: #arch 1&% 2&14

Journal of Petroleum Science and Technology 2014 , 41/% 2&028 h,,p:jps,.ripi.ir

2&14 !esearch 3(s,i,,e o) e,rolem 3(ds,r$ !33/

20

IN SITU SILICA SUPPORTED METALLOCENE CATALYSTS FOR

ETHYLENE POLYMERIZATION

Saeid Ahmadjo1* !assan Ara"i1 #holam$!ossein %ohuri2 #holam$&e'a (eja"at1 )ojta"amid+ar

1 )ostafa Ahmadi

, and Seyed )ohammad )ahdi )orta'a+i

1

1 apar,me(, o) a,al$s,% 3ra( ol$mer a(d e,rochemical 3(s,i,,e 33/% Tehra(% 3ra(

2 epar,me(, o) hemis,r$% Facl,$ o) Scie(ce% Ferdosi (i"ersi,$ o) #ashhad% #ashhad% 3ra(

' epar,me(, o) ol$mer E(i(eeri( a(d olor Tech(olo$% Amira-ir (i"ersi,$ o) Tech(olo$% Tehra(% 3ra(

ABSTRACT

;is20!0i(d/<rl2 !: = or phe($l/ as sppor,ed o( di))ere(, ,$pes o) silica -$ i( si, impre(a,io(

me,hod a(d sed )or e,h$le(e pol$meri>a,io(. 3( ,his me,hod% ,he s,ep o) ca,al$s, loadi( o(

sppor, as elimi(a,ed a(d commo( al$l almi(m ,riiso-,$lalmi(m% Ti;A/ coca,al$s, assed i(s,ead o) epe(si"e me,h$l almi(imoa(e #A?/ coca,al$s, i( ,he pol$meri>a,io(. The

e))ec, o) sr)ace area o) silica o( ,he per)orma(ce o) ,he sppor,ed ca,al$s,s si( ,hree di))ere(,

,$pes o) silica i(cldi( E12 '9& m2r./% '&6& 57& m

2r./ a(d ##041 11&& m

2r./ as

i("es,ia,ed. The sr)ace area had a more cri,ical role rela,i"e ,o o,her charac,eris,ics o) ,he

sppor, i( ,he per)orma(ce o) ca,al$s,s. ;$ si( ##041 as sppor,% ,he i(e,ic s,a-ili,$ as

e(ha(ced. The ac,i"i,$ o) ,he sppor,ed ca,al$s,s as i(creased -$ i(creasi( ,he sr)ace area o)

silica i( ,he order o) ##041 '&6& E12. The morpholo$ o) pol$mer par,icles as impro"ed

a(d reac,or )oli( as elimi(a,ed -$ sppor,i( ,he ca,al$s,.

-ey.ords: 3( Si, 3mpre(a,io(% =e,eroe(eos a,al$sis% #e,alloce(e% ol$e,h$le(e% Silica

INTRODUCTION

ol$ole)i(s are ,he mos, idel$ sed pol$mers

a(d ,heir orld co(smp,io( eceeded 1&&

millio( ,o(s i( 2&1& B1C. Di,ho, a($ do-,% i,

ca( -e me(,io(ed ,ha, pol$meri>a,io( ca,al$s,s

pla$ ,he mos, "i,al role i( pol$ole)i( i(ds,r$ B20

4C. Amo( ,he (meros de"elopme(,s i(

pol$ole)i( ca,al$s,s% ,he disco"er$ o) me,al0

oce(e ca,al$s, is o(e o) ,he mos, crcial o(es

B5%6C. 3( ,he prese(ce o) #A? as coca,al$s,%

,hese ,$pes o) ca,al$s,s sho a co(sidera-l$

hih ac,i"i,$ )r,hermore% ,heir (ie co(,rol

o"er pol$mer micros,rc,re a(d prodci( (e

pol$mers mae ,hem as a promisi( ca,al$s, )or

"arios prposes B709C.

=oe"er% ,he homoe(eos me,alloce(e ca,a0

l$s,s ha"e some major dra-acs ,he lac o)

pol$mer morpholo$% reac,or )oli(% i(come0

pa,i-ili,$ i,h (e processes% a(d )i(all$ ,heir

e,reme co(smp,io( o) epe(si"e #A? as

coca,al$s, are o) mai( co(cer(s B1&016C. To

o"ercome ,hese pro-lems% di))ere(, approachesha"e -ee( sed% amo( hich ,he immo-ile0

>a,io( o) me,alloce(e ca,al$s, o( a sppor, has

-ee( o(e o) ,he -es, sol,io(s B17% 18C.

reser"i( ,he ad"a(,aes o) ,he homoe(eos

ca,al$s, hile ,he ca,al$s, is a(chored ,o a

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Journal of Petroleum3( Si, Silica Sppor,ed #e,alloce(e a,al$s,s G Science and Technology

Journal of Petroleum Science and Technology 2014% 41/% 2&028 h,,p:jps,.ripi.ir


/ 21

sppor, is ,he e$ poi(, hich has -ee( )ocsed

o( i( ,he las, decade.

As repor,ed i( ,he li,era,re B6%7%19C% ,he ro,e

o) a(chori( me,alloce(e ca,al$s,s a(d ,he

(a,re o) ,he sppor, pla$ ,he e$ roles i( ,heca,al$s, ac,i"i,$ a(d )i(al proper,ies o) ,he

pol$mer. There are a, leas, ,hree -asic me,hods

)or sppor,i( me,alloce(e ca,al$s,s hich

i(clde:

10

Sppor,i( ,he me,alloce(e a(d ,he(

reac,i( i,h almi(oa(e direc, me,hod/

20

Sppor,i( ,he almi(oa(e a(d ,he(

reac,i( i,h ,he me,al comple i(0

direc, me,hod/

'0

3mmo-ili>i( me,alloce(e compo(d o(

sppor, ,hroh co"ale(, ,e,hers B7%11%

2&C.

To ,he -es, o) or (olede% p ,o (o% mos,

o) a,,e(,io( has -ee( )ocsed o( )i(di( ,he

-es, sppor,i( me,hods a(d procedre

co(di,io(s B21C% hile ,he i("es,ia,io( o) ,he

e))ec,s o) ph$sical charac,eris,ics o) sppor,s

sch as sr)ace area% pore si>e% a(d pore "olme

o( ,he per)orma(ce o) sppor,ed ca,al$s,s

)orms a "er$ small por,io( o) ,hese ors B220

24C.

3( ,he prese(, s,d$% ,he i( si, impre(a,io(

me,hod as sed ,o immo-ili>e ;is20!0

i(d/<rl2!: = or he($l/ o( di))ere(, ,$pes o)

silica. ;$ si( ,his me,hod% ,he prepara,io(

complei,ies e(co(,ered i( ,he ,radi,io(al

me,hods o) sppor,i( me,alloce(e ca,al$s,s

sch as direc, me,hod% i(direc, me,hod% a(d

co"ale(, ,e,heri( me,hod ca( -e o"ercome B25%

26C. 3( ,his ,ech(ie% ,he s,ep o) ca,al$s, loadi(

o( sppor, as elimi(a,ed a(d a commo( al$l

almi(m Ti;A/ as sed i( ,he pol$meri>a,io(

B27%28C. !eardi( ,he (a,re o) ,his me,hod% ,he

e))ec, o) sppor, ,$pe o( ,he per)orma(ce o) ,he

immo-ili>ed ca,al$s, i( e,h$le(e pol$meri>a,io(

as )r,her i("es,ia,ed.

EXPERIMENTALS

Materials

Three ,$pes o) silica i(cldi( ##041% 0'&6&%

a(d E012 ere sed i( ,he crre(, or.

Spherical ##041 sppor, as s$(,hesi>ed

accordi( ,o Heooma(esh e, al. B29C 0'&6&as spplied -$ o. a(d E012 as pro"ided

-$ ross)ield o. #e,h$lalmi(oa(e #A?/ i(

,ole(e 1& ,.I/ a(d ,riiso-,$lalmi(m Ti;A/

ere spplied )rom Aldrich. ;is20!0i(d/<rl2!: =

or he($l/ as s$(,hesi>ed accordi( ,o ,he

procedre repor,ed elsehere B'&C. Tole(e a(d

hep,a(e ere dried o"er al2 -$ dis,illa,io(. All

,he ma(ipla,io( i("ol"i( air a(dor a,er

se(si,i"e compo(ds ere per0)ormed (der ,he

a,mosphere o) dried H2 i( a lo"e -o.

Support Treatment

Ta-le 1 shos ,he ph$sical proper,ies o) ,he

,hree ,$pes o) silica emplo$ed. As see( i( Fire

1 a(d Ta-le 1% ,he ##041 par,icles ere i( a

(a(o ra(e i,h a hih sr)ace area% hile ,he

si>e o) E12 a(d par,icles as i( ,he order o)

microme,er. 3( addi,io(% ,he imaes o) sppor,s

re"ealed ,ha, ,he 0'&6& a(d ##041

par,icles had a spherical shape% hile ,he

morpholo$ o) E012 as irrelar. For ,he

prepara,io( o) silica pre,rea,ed i,h #A?% )irs,

5 rams o) silica as calci(a,ed (der ,he

a,mosphere o) H2 a, 25& J )or 5 hors. The(% 1

ram o) ,he deh$dro$la,ed silica as ss0

pe(ded i( ,ole(e. A),erards% 4 ml o) #A? 1&

,.I i( ,ole(e/ as added ,o ,he sspe(sio(

a(d s,irred o"er (ih,. Fi(all$% ,he silica as

ashed i,h ,ole(e a(d hep,a(e )or ,imesa(d ,he )i(al sspe(sio( as sed as ,he

sppor, i( ,he pol$meri>a,io( s,ep.

Polymerization

E,h$le(e homopol$meri>a,io( as carried o, i(

a 10li,er ;chi reac,or ;chilas,er -md '&&/

eipped i,h )ll$ co(,rolled s$s,ems o) ,emp0

era,re% s,irri( speed% reac,io( pressre% a(d

mass )lo o) mo(omer. n0=ep,a(e as

i(,rodced i(,o ,he reac,or 4&& ml/ a(d as

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Science and Technology S. Ahmadjo% =. Ara-i% Kh. =. <ohri% Kh. !. Heja-a, e, al.



22 /

sa,ra,ed i,h e,h$le(e a, ,he reac,io( ,emp0

era,re. Ti;A as a sca"e(er/% #A?0modi)ied

silica% a(d ,he ca,al$s, sol,io(s ere added

respec,i"el$. A, ,he e(d o) ,he pol$meri>a,io(

mai(l$ a),er '& mi(/% ,he co(,e(, o) ,he reac,oras pored i(,o a( ecess amo(, o) me,ha(ol%

)olloed -$ )il,eri( a(d dr$i( o"er(ih,.

igure 1 S) images of the supports3 a5 P6$,070

magnification of 40853 "5 P$12magnification of

100853 c5 )C)$41 magnification of 2000859

Ta"le 1 Te:tural properties of the supports

Silica Surface aream

29gr9

$15

Pore +olumecm

,9gr9

$15

Pore diameternm5

E12 '9& 1.75 18

'&6& 57& '.&& 21

##041 11&& &.5& 2

Characterization

For measri( ,he sr)ace area o) ,he silica sam0

ples% ,he$ ere o,assed 1&02

m-ar/ a, 8& J

)or a, leas, 8 hrs. Adsorp,io(0desorp,io( (i,ro0e( iso,herms ere recorded a, L196 J i( a

Kemi(i 2'75 #icromeri,ics% Horcross% .S.A./.

Speci)ic sr)ace areas ere de,ermi(ed -$ ,he

;r(aer0Emme,,0Teller ea,io( PP&M&.&50&.'5/%

hile ,he pore "olmes a(d pore diame,ers

ere de,ermi(ed i,h ,he ;are,, *o$(er

=ale(da ;*=/ me,hod. The mel,i( poi(, o) ,he

pol$mer as measred si( S N model STA

78&/ a(d Al co(ce(,ra,io( as measred -$

i(dc,i"el$ copled plasma 3/ model 7'50ES

Oaria( o./. Fi(all$% ,he morphol0oies o) ,he

sppor,s a(d pol$e,h$le(e samples ere

mo(i,ored -$ a sca((i( elec,ro( microscope

OEKA E#3TE= P45&Q% >ech !ep-lic/ a),ercoa,i( ,he samples i,h a ,hi( la$er o) old.


Effect of Polymerization Conditions on

the Performance of Bis(2-R-ind)ZrCl2 (R:

H or, Phenyl) /SiO2 (PQ 3060)

The resl,s prese(,ed i( Ta-le 2 sho ,he

depe(de(ce o) pol$meri>a,io( -eha"ior o(

reac,io( ,empera,re a(d mo(omer co(ce(,ra0,io(. The lo ac,i"i,ies a, ,empera,res a-o"e

6& J ca( -e a,,ri-,ed ,o ,he i(crease o)

deac,i"a,io( ra,e co(s,a(,s a(d% co(see(,l$%

,he deac,i"a,io( o) ac,i"e si,es pro-a-l$ -$

cha(i( ,heir s,rc,re B'1% '2C. A hiher

ca,al$s, ac,i"i,$ as o-,ai(ed a, hiher

mo(omer pressres i, ca( -e s,a,ed ,ha, -$

i(creasi( ,he pol$meri>a,io( pressre ,he

mo(omer co(ce(,ra,io( i(creased i( ,he reac0

,io( medim% hich led ,o a rise i( ,he prodc,0

i"i,$ o) ,he s$s,em B''0'5C. These resl,s also

i(dica,e ,ha, ,he ac,i"i,ies o) ,he sppor,ed

ca,al$s,s are loer compared ,o homoe(eos

co(,erpar,s i,h a redc,io( o) #A? co(smp0

,io(.

Fires 2 a(d ' sho ,he e))ec, o) pol$meri>e0

,io( ,empera,re a(d e,h$le(e pressre o(

pol$meri>a,io( ra,e respec,i"el$. As see(% ,he

i(e,ics o) ,he sppor,ed ca,al$s,s are s,ill o) ,he

deca$ ,$pe% hich is re)lec,ed i( ,he deca$ i(de

31/ resl,s Ta-le 2/.

=oe"er% ,he co("ere(ce o) 3 "ales ,oard

(i,$% i( compariso( ,o homoe(eos ca,al$s,s%

co()irms ,he i(creased ca,al$s, s,a-ili,$. This

impro"eme(, ca( -e a,,ri-,ed ,o ,he elimi(a0

,io( o) -imoleclar deac,i"a,io( -$ sppor,i(

,he ca,al$s, B'6%'7C.

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/ 2,

Ta"le 2 thylene polymeri'ations using P6$,070 silica supported catalyst

Type of catalysta Catalyst mol5 ;Al<)A;%r< Pressure "ar5 Tp =C5 Acti+ity >g P?mol %r9hr55 @

"

1 A 'R1&06

4&&:1 4 5& 5867 '.&

2 A 'R1&06

4&&:1 4 6& 7''' 2.'

' A 'R1&06 4&&:1 4 7& 65'' 2.7

4 A 'R1&06

4&&:1 4 8& 4''' 2.5

5 A 'R1&06

4&&:1 6 6& 1&667 2.7

6

Ao 1R1&06

5&&&:1 6 6& 4&&&& 8.6

7 ; 6R1&06

4&&:1 6 6& 27&& '.'

8 ; 6R1&06

4&&:1 6 7& '&'' 0

9 ; 6R1&06

4&&:1 6 8& 18'' 0

1& ;o 'R1&06

2''':1 6 6& 1&8&& 1&

ol$meri>a,io( co(di,io(s: ,imeM '& mi( (0hep,a(eM4&& ml BTi;ACM1.5 mmol as a sca"e(er/.a T$pe A: ;is3(d<rl2Si?2 /% Ao: ,he homoe(os )orm o) A% ,$pe ;: ;is2h3(d<rl2Si?2 /% ;o: ,he homoe(os

)orm o) ;.- 3: deca$ i(de: R p a, maimmR p a, ,he e(d o) reac,io( 3M R pmaimm/R p'& mi(//

igure 2 -inetic profiles of ethylene polymeri'ation

.ith Bisnd%rCl2?Silica P6$,0705 sho.ing the effect

of polymeri'ation temperature

The morpholo$ o) pol$mer par,icles depic,ed i(

Fire 4 shos ,ha, ,he sppor,ed ca,al$s,

prodces spherical pol$mer par,icles% replica,i(

,he i(i,ial shape o) sppor, par,icles ,his is i(

accorda(ce i,h ,he replica,io( phe(ome(o(

a(d (o e"ide(ce o) reac,or )oli( ca( -e )o(d

B21%'8%'9C. 3( co(,ras,% ,he shape o) ,he pol$mer

prodced -$ ,he homoe(eos ca,al$s, as

comple,el$ irrelar.

Effect of Polymerization Conditions on the

Performance of Bis(2-R-ind)ZrCl2 (R:H or

Phenyl)/SiO2 (MCM-41)

The pol$meri>a,io( resl,s ,a-la,ed i( Ta-le '

clearl$ i(dica,e ,he impro"eme(, achie"ed i(

,he per)orma(ce o) ,he immo-ili>ed ca,al$s, -$

si( ##041 as a sppor,.

igure , -inetic profiles of ethylene polymeri'ation

.ith Bisnd%rCl2?Silica P6$,0705 sho.ing the effect

of monomer pressure

3 "ales sho ,ha, ,he ca,al$s, sppor,ed o(

##041 is s,a-ler ,ha( ,he o(e sppor,ed o(

'&6&. 3( o,her ords% -$ cha(i( ,he ,$pe o)

,he sppor,% ,he i(e,ic cr"es ere shi),ed

)rom deca$ ,$pe ,o s,a-le ,$pe. =oe"er% ,he

morpholo$ o) pol$mer par,icle as irrelar%

hich as pro-a-l$ de ,o ,he (a(o si>e o) ,he

sppor, par,icles casi( pol$mer par,icles ,o

alomera,e B29C.

time s5

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24 /

igure 4 )orphology of polymer particles synthe$

si'ed "y a5 Bisnd%rCl2 homogenous form and "5

Bisnd%rCl2?Silica P6$,0705

He"er,heless% ,he o-ser"ed spherical )loccles i(

Fire 5 pro"e ,ha, ,he replica,io( phe(ome(o(

has de)i(i,el$ occrred. The ac,i"i,$ o) ,he

s-s,i,,ed i(de($l -ased sppor,ed ca,al$s,

'&&& E.mol <r01

.hr01

/ is less ,ha(

;is3(d<rl21&&&& E.mol <r01

. hr01

/% hich

ca( -e a,,ri-,ed ,o elec,ro(ic a(d s,eric e))ec,so) ,he s-s,i,e(,s o( ,he per)orma(ce o) ,he

ca,al$s, B4&C.

igure )orphology of polymer particles synthe$

si'ed "y Bisnd%rCl2?Silica )C)$4159 )agnification

of 200085

Ta"le , thylene polymeri'ations using )C)$41 supported catalyst

Type of Catalysta Catalyst mol5 ;Al<)A;%r< Pressure "ar5 Tp =C5 Acti+ity >g P?mol %r9hr55

@

"

1 5R1&06

24& 4 6& 728& 1.2

2 5R1&06

24& 4 7& 852& 0

' 1R1&05

12& 6 6& 11'&& 1

4

Ao 1R1&06

5&&& 6 6& 4&&&& 8.6

5 1R1&05

12& 6 5& 7&& 0

6 1R1&05

12& 6 6& 1'&& 1.8

7 1R1&05

12& 6 7& 86& 0

8

;o 'R1&06

2''' 6 6& 1&8&& 1&

ol$meri>a,io( co(di,io(s: ,imeM'& mi( =ep,a(eM4&& ml BTi;ACM1.5 mmol as a sca"e(er/a T$pe : ;is3(d<rl2Si?2 ##/% Ao: ,he homoe(os )orm o) % ,$pe : ;is2h3(d<rl2Si?2 ##/% ;o: ,he

homoe(os )orm o) .- 3: deca$ i(de: R p a, maimmR p a, ,he e(d o) reac,io( 3M RpmaimmRp'& mi(/

Effect of the Surface Area of Support

The Al co(,e(, o) ,he modi)ied sppor,s%

de,ermi(ed -$ 3 Ta-le 4/% clearl$ shoed ,ha,

i(creasi( #A? co(ce(,ra,io( i(creased ,he

amo(, o) ra),ed Al. 3, as o-ser"ed ,ha,

##041 i,h a speci)ic sr)ace area a-o"e 1&&&

m2.r.

01 as more capa-le o) hos,i( Al. 3, is

o-"ios ,ha, -$ i(creasi( ,he sr)ace area% ,he

8/11/2019 Jpst 2014 Vol. 4 No. 1





/ 2

accessi-ili,$ o) ?= rops o) ,he sppor, rises

a(d% co(see(,l$% ,he pro-a-ili,$ o) loadi( Al

is e(ha(ced.

Ta"le 4 Al contents determined "y CP

Type ofSupport

nitial Aluminummmol9gr9 silica

$15

Doaded Al.t9E5

0'&6& ' 00

0'&6& 6 9.1

0'&6& 12 12.2

##041 ' 5.2

##041 6 9.5

##041 12 1'.6

Ta-le 5 shos ,ha, ,he sr)ace area ca( pla$ a

e$ role i( ,he per)orma(ce o) ,he ca,al$s,. 3,

as o-ser"ed ,ha, he( ,he sr)ace area o) ,he

ca,al$s, as i(creased% ,he ac,i"i,$ o) ca,al$s,

as raised ,oo% si(ce i, i(creased ,he pro-a-ili,$

o) co(,ac, -e,ee( ac,i"e ce(,ers a(d sp0

por,ed #A? B41C. (do-,edl$% ,he hiher

s,a-ili,$ o) ,he i(e,ic pro)ile o) ,he ca,al$s,

sppor,ed o( ##041 Fire 6/ ca( -e rela,ed

,o ,he -e,,er accessi-ili,$ o) ,he ac,i"e ce(,ers

dri( pol$meri>a,io(. 3, seems ,ha, i( ,he i(

si, sppor,ed ca,al$s,s (e ca,al$,ic si,es are

co(,i(osl$ )ormed o( ,he e,er(al sr)ace o)

,he silica par,icles -$ ,he a-sorp,io( o) ,he

ca,al$s, compo(ds hich are a"aila-le i( ,he

liid phase dri( pol$meri>a,io( B42C. The

s,dies o) Soa B4'C a(d Da(e B24% 44C ha"e

co()irmed ,he domi(a(, role o) ,he pore "olme

o) sppor, o( ca,al$s, ac,i"i,$% hereas ,he

e))ec, o) sr)ace area has (o, -ee( ,ae( i(,o

acco(,. The impor,a(ce o) ,he sr)ace area-ecomes more domi(a(, i( ,he i( si, im0

pre(a,io( me,hod i( compariso( ,o ,he

,radi,io(al ,ech(ies% si(ce ,he co(,ac, ,ime

-e,ee( ,he ca,al$s, species a(d ac,i"a,ed

sppor, dras,icall$ decreases.

Ta"le ffect of surface area on the performance of Bisnd%rCl2 catalyst in ethylene polymeri'ation

Type of support

Surface area

m29gr9

$15

Acti+ity

>g P9mol %r9hr5$1

5

T m =C5 Crystallinity E5

E012 '5& 17&& 1'6.5 0000'&6&

57& 57&& 1'8.1 51.2

##041 11&& 11'&& 14&.4 55

ol$meri>a,io( co(di,io(s: =ep,a(eM4&& ml BAlTi;ACM2 mmol as a sca"e(er/ M6 -ar BAl#A?CB<rCM12&:1 B<rCM1R1&05

mol

igure 7 ffect of the type of support on the >inetic

profiles in the polymeri'ation of ethylene

CONCLUSIONS

The e))ec,s o) pol$meri>a,io( co(di,io(s a(d

sppor, speci)ica,io(s o( 3(de($l0-ased sppor,ed

me,alloce(e ca,al$s,s ere i("es,ia,ed. The

;is3(d<rl2Si?2 / sp0por,ed ca,al$s, shoed

,he hihes, ac,i"i,$ 1&&&& Emol <r.hr// a,

6& J a(d 6 -ar. The ca,al$s, i,h s-s,i,,ed

i(de($l lia(d 20 phe($l i(de($l/ shoed a loer

ac,i"i,$ '&&& Emol <r.hr.// ,ha( i,s (o(0

s-s,i,,ed co(,erpar,. The morpholo$ o)pol$mer par,icles as impro"ed a(d reac,or

)oli( as elimi(a,ed -$ sppor,i( ,he ca,al$s,.

3, as o-ser"ed ,ha, ,he co(smp,io( o) #A? as

decreased -$ sppor,i( ,he ca,al$s, ,he ra,io o)

Al ,o <r BAlC:B<rC/ decreased )rom 5&&& ,o loer

,ha( 5&&. The ac,i"i,$ o) ;is3(d<rl2 ca,al$s,

sppor,ed -$ ,he i( si, impre(a,io( me,hod as

i("es,ia,ed si( ,hree ,$pes o) sppor,s. The

;is3(d<rl2##041 shoed ,he hihes, ac,i"i,$%

hich as ,ice as lare as ,he 0'&6& a(d E012

8/11/2019 Jpst 2014 Vol. 4 No. 1






27 /

sppor,ed ca,al$s,s. ##041 sppor, -$ ,he

sr)ace area o) 11&& m2.r.

01 shoed a ca,al$s,

ac,i"i,$ o) 11.' Emol <r.hr//% hile ,he micro0

si>ed sppor,s% (amel$ 0'&6& a(d E012% i,h

,he respec,i"e sr)ace area o) 59& a(d '9& m2

.r.01

shoed a ca,al$s, ac,i"i,$ o) 5.6 a(d 1.7

Emol <r.hr// respec,i"el$. 3, as co()irmed ,ha,

,he sr)ace area o) ,he sppor, had ,he mos,

crcial e))ec, o( ,he per)orma(ce o) ,he i( si,

sppor,ed ca,al$s,s. This -eha"ior ca( -e a,,ri-0

,ed ,o ,he decreased co(,ac, ,ime dri( ca,al$s,

impre(a,io( i( ,his me,hod% hich ampli)ies ,he

impor,a(ce o) ,he pro-a-ili,$ o) ,he co(,ac,

-e,ee( ca,al$s, compo(ds a(d ,he e,erior

po,e(,ial impre(a,io( si,es.

NOMENCLATURE

;*= ;are,, *o$(er =ale(da

;is3(d<rl2 ;isi(de($l/>irco(imdichloride

;is2h3(d<rl2 ;is20phe($l i(de($l/>irco(im

dichloride

3 eca$ i(de

3 3(dc,i"el$ copled plasma

#A? #e,h$l almi(imoa(eTi;A Triiso-,$lalmi(m

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B11C

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8/11/2019 Jpst 2014 Vol. 4 No. 1





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E,h$le(e ol$meri>a,io( i,h Silica0

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*o(somji, ;.% Hamposri S.% a(d

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B16C

#ares #. F. O. a(d o(,e A.% The

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B17C o,hira, T.% *o(somji, ;.% a(d

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Si?20 a(d <r?20sppor,ed <irco(oce(e

#A? a,al$s,s o( E,h$le(e10ole)i( o0

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Z0ole)i(s o( Kas0phase E,h$le(e ol$0

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E,h$le(e010hee(e opol$mers #ade

i,h Sppor,ed #e,alloce(e a,al$s,s:

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sppor,ed #e,alloce(e#A? a,al$s, i(

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Macromol .% 200% 3'% 467'04678.

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"ia i))ere(, ore Si>ed Silica0-ased0

sppor,ed <irco(oce(ed##A? a,a0

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;ia(chi(i .% Al"es #. . #.% e, al.%

harac,eri>a,io( a(d E"ala,io( o) Sp0

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>irco(im ichloride o( E,h$le(e ol$0

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opol$meri>a,io( o) 10hee(e a(d

E,h$le(e i( ,he Kas hase i,h (0

;p/2<rl2 o( Sppor,s i,h i))ere(,

ore Si>es%X Polymer % 200,% ""% 47910

48&'.

B25C Sil"eira F.% Al"es #. . #.% S,edile F. .%

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Te,re o( ,he S,rc,re o) Sppor,ed

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B26C

Sil"eira F.% e,r$ . F.% o>e-o( .% erherS. ;.% e, al.% Sppor,ed #e,alloce(e o(

#esoporos #a,erials%X Appl. Catal. A:

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B27C

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S,d$ o) rop$le(e ol$meri>a,io( si(

#e2Si!3(d/2<rl2Si?2eS#A?Al!' a(d

#e2Si !3(d/2<rl2#A? !M#e%=/%X Poly

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B28C

Fra(ceschi(i F. .% Ta"ares T. T. !.% Kreco

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B29C

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Emami #.% e, al.% repara,io( o)

ol$e,h$le(e Ha(o)i-ers si( !od0lie

##041Til4#l2T=F ;i0sppor,ed

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B'&C

#or,a>a"i #. #.% Ara-i =.% <ohri K. =.%

Ahmadjo S.% e, al.% E,h$le(e =omo0 a(d

8/11/2019 Jpst 2014 Vol. 4 No. 1






2F /

opol$meri>a,io( si( a ;is03(d<rl2

#e,alloce(e a,al$s,: S,rc,ral omposi0

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Macromol. React. )ng.% 2011% 3% 26'027&.

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E,h$le(e ol$meri>a,io( o(di,io(s o(

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;ers,ra #. F. a(d Deicer, K.% E,h$le(e

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e(eos #e,alloce(e a,al$s,0compari0

so( o) Kas a(d Slrr$ hases%X Macromol.

Mater. )ng.% 200% (*% 61&062&.

B'5C

Sha( . N. .% Soares *. ;. .% a(d e(lidis

A.% E,h$le(e10oc,e(e opol$meri>a,io(

S,dies i,h 3( si, Sppor,ed #e,allo0

ce(e a,al$s,s: E))ec, o) ol$meri>a,io(

arame,ers o( ,he a,al$s, Ac,i"i,$ a(d

ol$mer #icros,rc,re%X J. Polym. Sci.

Part A: Polym. Chem.% 2002% "*% 44260

4454.

B'6C

Ad>a *. A. #. a(d Tai, . *. T.% The

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opol$meri>a,io( si( =omoe(eos

a(d Silica0sppor,ed p2<rl2#A?

a,al$s, S$s,ems: Some 3(sih,s )rom ,he

Pi(e,ics o) ol$meri>a,io(% Ac,i"e e(,er

S,dies% a(d ol$meri>a,io( Tempera0

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B'7C Da( D.% Da( N.% Da( *.% #a <h.% e, al.%

S,d$ o( E,h$le(e co/ol$meri>a,io(

a(d i,s Pi(e,ics a,al$>ed -$ a !e"ersi-le

rossli(ed ol$s,$re(e0sppor,ed #e,al0

loce(e a,al$s,%X J. Appl. Polym. Sci .% 200%

($ % 16'2016'6.

B'8C ash,i A.% !ama>a(i A.% =iraoa Y.% Pim

SY.% e, al.% Pi(e,ic a(d #orpholoical

3("es,ia,io( o( ,he #a(esim E,hoide0

-ased <ieler Ha,,a a,al$s, )or rop$le(e

ol$meri>a,io( si( T$pical E,er(al

o(ors%X Macromol. Symp.% 200H% '!% 520

57.

B'9C Ahmadi #.% *amjah !.% Heooma(ehs #.%

<ohri K. =.% e, al.% <ieler0Ha,,a

#e,alloce(e =$-rid a,al$s, )or E,h$le(e

ol$meri>a,io(%X Macromol. React. )ng.%

200G% % 6&4061&.

B4&C oa,es K. D. a(d Da$mo,h !. #.%

?scilla,i( S,ereoco(,rol: a S,ra,e$ )or

,he S$(,hesis o) Thermoplas,ic Elas,o0

meric ol$prop$le(e%X Science.% 1HH% 6$ %2170219.

B41C ;ram-illa !.% !ad,e .% S,edile F. .% os

Sa(,os *. =. <.% e, al.% #e,alloce(e

a,al$s, Sppor,ed o( Silica[ma(esia

Qeroels )or E,h$le(e ol$meri>a,io(%X

Appl. Catal. A: -en.% 2010% 3'% 1&60114.

B42C

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opol$meri>a,io( harac,eris,ics o)

=omoe(eos a(d 3( Si, Sppor,ed

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#a,erials ,o Adsorp,i"e Separa,io( o)

#e,h$lalmoa(e sed as o0ca,al$s, i(

?le)i( ol$meri>a,io(%X Micoropor.

Me&opor. Mat .% 2001% """!% 5570564.

B44C

Pmae .% Da(e S. E.% raser,hdam .%

a(mah .% e, al.% !a,es a(d rodc,

roper,ies o) ol$e,h$le(e rodced -$

opol$meri>a,io( o) 10hee(e a(d

E,h$le(e i( ,he Kas hase i,h (0

;p/2<rl2 o( Sppor,s i,h i))ere(,

ore Si>es%\ J. Appl. Polym. Sci .% 200,% '$ %

116101177.

8/11/2019 Jpst 2014 Vol. 4 No. 1




Asghar Molaei Dehkordi


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

8/11/2019 Jpst 2014 Vol. 4 No. 1



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


+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

8/11/2019 Jpst 2014 Vol. 4 No. 1


Journal of Petroleumiodesulfuri;a,io( of *imula,ed Bigh, uel il J Science and Technology



, +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.


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.

8/11/2019 Jpst 2014 Vol. 4 No. 1






+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

8/11/2019 Jpst 2014 Vol. 4 No. 1





, ++

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


7&P

8/11/2019 Jpst 2014 Vol. 4 No. 1






+4 ,

,es of mi%roorga(isms C18) 21.

&igure 4- .ffect of initial <T concentration on the


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""


<T concentration 8ppm9

8/11/2019 Jpst 2014 Vol. 4 No. 1





, +>

&igure >- Predicted ersus actual alues of the


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 Jpst 2014 Vol. 4 No. 1






+: ,

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 Jpst 2014 Vol. 4 No. 1





, +@

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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uels - Dee Desulfuri;a,io( a(d Dee

Dearoma,i;a,io( of Middle Dis,illa,es)W i(:

=su) 7. *.) $o-i(so() . $. /Eds.0) Practical

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C12 Mehr(ia M. $.) o(akdarour .) To<fighi

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era,io(al Ase%,s of Airlif, iorea%,ors

for e,roleum iodesulfuri;a,io()W +n-iron.

Prog., 2004) &', 2"6214.

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7omou(ds a(d ,he Mi!,ure of DT + 4)6

DMDT - M%o-a%,erium s. [D19)W

Bioresource Technol .) 2005) ) #6#"

#6#4.

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+5 ,

C14 Da&oodiDehagha(i .) Sosoughi M.) a(d

[iaee A.) Viodesulfuri;a,io( of Di-e(;o

,hiohe(e - a >e<l sola,ed $hodo

%o%%us Er,hroolis *,rai()W Bio/resource

Technol., 2010) !0!) 11"211"5.

C15 Bi K.) Ka(g M.) 7he( =.) 7he( '.) e, al.)

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- Hro<i(g 7ells of Hordo(ia s. i( a,%h

7ul,ures)W Biotechnol. (ett .) 200:) &))

115119.

C16 *ha&a(di M.) *adeghi;adeh M.) [omorodi

our A.) a(d Gha3eh Gh.) Fiodesulfuri;a

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Hordo(ia Alka(i&ora(s $9"A)W Bio/

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C1 A--adA(daloussi *.) Bag(el 7.)Kar;<oda M.) a(d Mo(o, .) VMul,i

%ri,eria 7omariso( of $es,i(g 7ell A%,i&i

,ies of a%,erial *,rai(s *ele%,ed for

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ou(ds)W +n1. $icro%. Technol .) 200+) '&)

446454.

C18 'ia N.) Ke( '.) *u( [.) 7aii( X.) e, al.)

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iors - $es,i(g 7ells of Hordo(ia s. KX

"1 a(d i,s Mu,a(, i( il<a,er

Disersio(s)W Chem. +ng. Sci., 200:) *!)1982""".

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moom A.) Ta(aka E.) e, al.) Viode

sulfuri;a,io( of =dro%ar-o(s a(d Diesel

uels - $hodo%o%%us s.W strain P'&C!)

Biochem. +ng. J., 2001) )) 151156.

C2" Mers $. =. a(d Mo(,gomer D. 7.)

Response Surface $ethodology: Process

and #ptimi1ation 2sing designed e3peri/

ment ) 2(d ed.) >e< Zork: Kile) 2002.

C21 7aro A.) ol,es G.) Be,\( .) a(d Har%]a

7al&o E.) VDi-e(;o,hiohe(e iodesulfur

i;a,io( i( $es,i(g 7ell 7o(di,io(s -

Aero-i% a%,eria)W Biochem. +ng. J.) 200@)

'") 19119.

C22 $am^re;7orredores. a(d A-hi3ee, . .)

VEmergi(g io%a,al,i% ro%esses) i(:

*,udies i( *urfa%e *%ie(%e a(d 7a,alsis)W

+lse-ier.) 200@) 65226.

C2# Huo-i( *.) 'ia(mi( N.) =uaii(g [.) a(d

=ui;hou B.) VDee Desulfuri;a,io( of

=drodesulfuri;ed Diesel il - seudomo(as Delafieldii $8)W J. Chem. Tech.

Biotechnol., 200>) )0) 42"424.

C24 Gaufma( E. >.) =arki(s '. .) a(d orole A.

.) V7omariso( of a,%h*,irred a(d

Ele%,rosra $ea%,ors for iodesulfuri;a

,io( of Di-e(;o,hiohe(e i( 7rude il a(d

=dro%ar-o( eeds,o%ks)W Appl. Biochem.

Biotechnol., 1995) 4') 12144.

C25 7aro A.) ol,es G.) Be,\( .) a(d Har%]a

7al&o E.) Viodesulfuri;a,io( of Di-e(;o

,hiohe(e - Hro<i(g 7ells of seudo

mo(as u,ida 7E7T 529 i( ihasi%

Media)W Chemosphere.) 2005) 4') 66#

669.

8/11/2019 Jpst 2014 Vol. 4 No. 1




Javad Ivakpour


Tel: +98 21 4825 5038

Fa:+98 21 44!3 9!38

Article history

"e#eived: $u%u&' 23( 2012

"e#eived i) revi&ed *orm: ovem,er 28( 2012

$##ep'ed: $u%u&' 0!( 2013

$vaila,le o)li)e: -ar# 10( 2014

Journal of Petroleum Science and Technology 2014 , 4/1( 3944 ''p:jp&'.ripi.ir

2014 "e&ear# I)&'i'u'e o* e'roleum I)du&'r /"II

3

DEVELOPING A NEW INITIALIZATION PROCEDURE FOR

DISTILLATION COLUMN SIMULATION

Ja!ad "!a#pour1* and $orolah %asiri2

1 "e*i)i)% 6ivi&io)( "e&ear# I)&'i'u'e o* e'roleum I)du&'r( Tera)( Ira)( .7. o: 1451998

2 ompu'er $ided ro#e&& E)%i)eeri)% ;a,( <#ool o* emi#al E)%i)eeri)%( Ira) =)iver&i' o* <#ie)#e a)d

Te#)olo%

ABSTRACT

Te &imula'io) o* di&'illa'io) #olum)& i& a) e&&e)'ial &'ep i) de&i%)( op'imi>a'io)( a)d ra'i)%. I) 'i&

paper( a )e? pro#edure a& ,ee) propo&ed *or 'e i)i'ial e&'ima'io) o* #olum) pro*ile& ,a&ed o)

modi*ied rem&erA& %roup me'od *or &imple a)dor #omple #olum)&. Te e**e#' o* 'i&

i)i'iali>a'io) al%ori'm o) &imula'io) pro#edure a& ,ee) &'udied 'rou% '?o eample&. Te

re&ul'& &o? &i%)i*i#a)' improveme)' i) #o)ver%e)#e a)d #o)&idera,le &avi)% i) ee#u'io) 'ime up

'o 30B. Te propo&ed me'od #a) ,e u&ed i) pro,lem& ?i# reCuire )umerou& &imula'io) ru)& 'o

*i)d 'e op'imum #o)di'io)& &u# a& di&'illa'io) #olum) &eCue)#i)% a)d 'e op'imum de&i%) o*

di&'illa'io) #olum)&. Te propo&ed me'od #ould al&o ,e u&ed a& a) approima'i)% &imula'io)

me'od *or &imple a)d #omple di&'illa'io) #olum)& #o)&ideri)% #o)&'a)' rela'ive vola'ili' a)d

#o)&'a)' molar over*lo? a&&ump'io)&.

%ey&ords: 6i&'illa'io)( <imula'io)( I)i'iali>a'io)( olum) ro*ile&( rem&erA& -e'od

INTRODUCTION

<imula'io) i& a ke &'ep i) di&'illa'io) #olum)

op'imi>a'io) pro,lem&. $##ura#( &peed( a)d

#o)ver%e)#e proper'ie& are 'ree impor'a)'

*a#'or& i) 'e &ele#'io) o* a proper &imula'io)

me'od. $##ura# depe)d& mai)l o) 'e di&'illa

'io) #olum) modeli)% a&&ump'io)& *ollo?ed , 'e

'ermi)a'io) #ri'eria i) &imula'io) &'ep&. "e%ardi)%

'e modeli)% a&&ump'io)&( 'e &imula'io) me'od&

are divided i)'o 'ree mai) me'od&( )amel

approima'ed( eCuili,rium ,a&ed( a)d ra'e,a&ed

me'od&. Te eCuili,rium ,a&ed me'od& are 'e

mo&' #ommo)l u&ed &imula'io) me'od& a)d are

,a&ed o) 'e eCuili,rium a&&ump'io) ,e'?ee)

leavi)% vapor a)d liCuid *lo?& *or ea# &'a%e. I)

'e&e me'od&( 'e #olum)& modeli)% eCua'io)&#alled -E<D #a) ,e &olved ?i' di**ere)'

pro#edure&. a&ed o) 'e &ele#'ed &olvi)%

pro#edure( di**ere)' eCuili,rium,a&ed &imula'io)

me'od& ave previou&l ,ee) propo&ed 1.

$l'ou% a lar%e )um,er o* me'od& ave ,ee)

propo&ed *or di&'illa'io) #olum) &imula'io)( 'e

la#k o* #o)ver%e)#e a)d #o)&idera,le &imula'io)

= 'ime are &'ill 'e #ommo) di**i#ul'ie& i) all

'e me'od&. Te&e di**i#ul'ie& ?ould ,e more&i%)i*i#a)' i) op'imi>a'io) pro,lem& ?e) a

lar%e )um,er o* &imula'io) ru)& are reCuired 'o

*i)d 'e op'imum #o)di'io)&G di&'illa'io) #olum)

&eCue)#i)% i& a ?ell k)o?) eample o* 'e&e

pro,lem&. I) 'i& 'pe o* pro,lem&( u&uall

8/11/2019 Jpst 2014 Vol. 4 No. 1



Science and Technology J. Ivakpour a)d . a&iri

Journal of Petroleum Science and Technology 2014( 4/1( 3944 ''p:jp&'.ripi.ir


40 '

&or'#u' de&i%) me'od& are impleme)'ed 2.

<or'#u' me'od& are developed ,a&ed o) '?o

mai) a&&ump'io)&( )amel #o)&'a)' molar over

*lo? a)d #o)&'a)' vola'ili'. Te&e a&&ump'io)&

are al&o made i) 'e approima'ed &imula'io)me'od& &u# a& rem&erH& %roup me'od u&ed

i) 'i& ?ork. e#au&e o* lo?er #ompu'a'io)

'ime( &or'#u' me'od& are &'ill u&ed ?idel i)

op'imi>a'io) pro,lem& 3. Do?ever( eCuili,rium

,a&ed model& like i)&ideou' al%ori'm #a) ,e

u&ed *or more a##ura'e re&ul'& i* &imula'io) 'ime

i& a##ep'a,le 4(5. Tere*ore( &or'er &imula'io)

'ime i& impor'a)' i) 'e&e pro,lem&.

Te *ir&' #ri'i#al &'ep i) di&'illa'io) #olum)

&imula'io) i& 'e i)i'ial a&&ump'io) o* #olum)

pro*ile&. -ore a##ura'e a&&ump'io)& #a) re&ul'

i) ,e''er #o)ver%e)#e a)d &or'er ee#u'io)

'ime. -ore impor'a)'l( poorer a&&ump'io)&

ma re&ul' i) 'e la#k o* #o)ver%e)#e. Ti& *a#'

i& more e**e#'ive i) #omple #olum)& ?i' &ide

&'ream& produ#'& a)dor mul'iple *eed &'ream&.

I) 'i& ?ork( a) i)i'iali>a'io) me'od a& ,ee)

propo&ed ,a&ed o) 'e approima'ed &imula'io)

me'od 5. Te propo&ed i)i'iali>a'io) al%ori'm a& ,ee) impleme)'ed i) 'e i)&ideou'

&imula'io) me'od. Ti& al%ori'm a& ,ee)

#ompared 'rou% '?o eample& ?i' 'e

&imple i)i'iali>a'io) al%ori'm *reCue)'l u&ed i)

o'er ?ork&. -oreover( 'i& al%ori'm a& ,ee)

#om,i)ed ?i' '?o di**ere)' dampi)% me'od&

'o make i' po&&i,le 'o *ur'er a)al>e 'e

propo&ed al%ori'm.

INITIALIZATION ALGORITHM ANDDAMPING METHOD

Initialization Algorithm

To &olve 'e -E<D eCua'io)&( 'e #olum)

pro*ile& mu&' i)i'iall ,e a&&umed. I' i& #lear 'a'

'e a&&ump'io)& ?i# are #lo&er 'o 'e 'rue

value& re&ul' i) le&& #ompu'a'io)al e**or' i) 'e

&olvi)% pro#edure. 7)e o* 'e ?ellk)o?)

i)i'iali>e'io) al%ori'm& /#alled &imple me'od

erei)( ,e#au&e o* i'& &impli#i' i& a& *ollo?&:

1()stimate the o!erall molar flo& ratesG 'e

overall molar *lo? ra'e& i) 'e #olum) #a) ,e

ea&il #ompu'ed , 'e #o)&'a)' molar over*lo?

a&&ump'io) 4.

2()stimate the temperature profileG , #om

,i)i)% 'e *eed &'ream&( 'e 'op a)d ,o''om

'empera'ure& #a) ,e a&&umed a& 'e de? a)d

,u,,le poi)'& o* 'e #om,i)ed *eed re&pe#'

'ivel. Te i)'ermedia'e &'a%e 'empera'ure& #a)

,e *ou)d , li)ear i)'erpola'io) ,e'?ee) 'e&e

'?o poi)'& 4.

3(Composition and %(!alue profilesG , *la&i)%

'e #om,i)ed *eed i&o'ermall a' 'e 'emp

era'ure o* ea# &'a%e( 'e #ompo&i'io) a)d value pro*ile& #a) ,e a&&umed 'rou% 'e

#olum)&.

Te di&'illa'io) #olum) #a) ,e divided i) a

)um,er o* &e#'io)& , 'e *eed &'ream& a)d

&ide&'ream produ#'&. Ea# &e#'io) i)#lude& a

)um,er o* &'a%e& a)d 'e e)'eri)% a)d leavi)%

vapor a)d liCuid &'ream&. Tere*ore( ea# &e#

'io) ?ould ave )o *eed or &ide&'ream a' i'&

&'a%e& a)d #a) #o)&eCue)'l ,e modeled , 'erem&erA& %roup me'od. I) 'e&e #o)di'io)&(

*eed &'ream& a)d &ide&'ream produ#'& #a) o)l

,e allo?ed a' 'e i)'ermedia'e &'a%e& ,e'?ee)

'?o &u##e&&ive &e#'io)&. Ivakpour a)d a&iri

propo&ed a) approima'ed &imula'io) me'od

*or 'e&e #o)di'io)& 5. Ti& approima'ed

&imula'io) me'od #a) ,e modi*ied 'o e&'ima'e

'e 'empera'ure a)d #ompo&i'io) pro*ile&

'rou% 'e #olum).

a&&umi)% 'e value& a' 'e i)'ermedia'e

'ra& a)d al&o a' 'e 'op a)d ,o''om o* 'e

#olum) /e.%. #o)&'a)' value 'rou% 'e

#olum) i) #om,i)ed *eed #o)di'io)&( 'e

approima'ed &imula'io) me'od #a) ,e &olved

'o de'ermi)e 'e i)'ermedia'e &'ream& a)d

produ#'& #ompo&i'io)&. Davi)% de'ermi)ed

'e&e value&( i' i& po&&i,le 'o modi* 'e value&

a' 'e de? poi)' o* leavi)% vapor &'ream *or

ea# i)'ermedia'e &'a%e. Te modi*ied value&

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Journal of Petroleum6evelopi)% a e? I)i'iali>a'io) ro#edure Science and Technology



' 41

#a) ,e u&ed *or re&olvi)% 'e approima'ed

me'od *or more a##ura'e re&ul'&. a&ed o) 'e

approima'ed &imula'io) al%ori'm( 'e i)i'ial

i>a'io) al%ori'm #a) ,e propo&ed a& *ollo?&:

1()stimate the o!erall flo& ratesG 'e overallmolar *lo? i) 'e #olum) #a) ,e e&'ima'ed ,

'e #o)&'a)' molar over*lo? a&&ump'io) a& i)

'e &imple me'od.

2(Composition and %(!alue profiles &olve 'e

approima'ed &imula'io) al%ori'm ?i' 'e

dou,le modi*i#a'io) o* value&. Davi)% de'er

mi)ed 'e e)'eri)% a)d leavi)% vapor a)d liCuid

#ompo)e)' *lo? ra'e& o* ea# &e#'io)( 'e

#ompo)e)' *lo? ra'e& o* ea# &'a%e #a) ,e

e&'ima'ed , li)ear i)'erpola'io). $*'er 'a'( 'e

value pro*ile #a) ,e e&'ima'ed , dividi)% 'e

value& o* vapor #ompo&i'io) 'o 'e #orre&po)d

i)% liCuid #ompo&i'io) *or ea# #ompo)e)'.

3()stimate the temperature profile: avi)%

de'ermi)ed 'e #ompo&i'io) pro*ile *rom 'e

previou& &e#'io)( 'e 'empera'ure #a) ,e e&'i

ma'ed a' 'e de? poi)' o* 'e leavi)% vapor

&'ream& o* ea# &'a%e.

Damping Method

Te dampi)% *a#'or i) varia,le& upda'i)% &'ep&

a& a &i%)i*i#a)' e**e#' o) 'e di&'illa'io) #olum)

&imula'io) re&ul'&. I) 'i& ?ork( 'e ,ou)di)%

me'od a& ,ee) u&ed *or 'e de'ermi)a'io) o*

dampi)% *a#'or . Ti& pro#edure #a) #o)&ider

a,l improve 'e #o)ver%e)#e a)d &peed o*

&imula'io) pro#edure&. Fur'ermore( 'e ?ell

k)o?) rode)A& dampi)% me'od a& ,ee)impleme)'ed i) 'e &epara'e model *or ,e''er

a)al>i)% 'e e**e#'& o* propo&ed i)i'iali>a'io)

al%ori'm o) 'e &imula'io) re&ul'& !.


Te e**e#' o* 'e propo&ed i)i'iali>a'io) me'od

a& ,ee) eami)ed i) 'i& &e#'io) 'rou% '?o

eample&. Te &pe#i*i#a'io)& o* 'e &'udied

eample& are &o?) i) Ta,le& 1 a)d 2. Te

e)%"o,i)&o) eCua'io) o* &'a'e a& ,ee) u&ed

*or predi#'i)% 'e eCuili,rium a)d e)'alp

#al#ula'io)&( i) 'e i)ve&'i%a'ed eample&. I)

'e&e eample&( #olum)& ave ,ee) &imula'ed

, *our di**ere)' model&. Te i)ve&'i%a'ed

model& are &imilar i) all 'e #ompu'a'io)al

pro#edure& e#ep' 'e dampi)% a)d i)i'iali>e

'io) al%ori'm&. I) ea# &pe#i*ied model( o)e o*

'e &'udied dampi)% me'od& /i.e. ou)di)% or

rode) a)d o)e o* 'e de&#ri,ed i)i'iali>a'io)

al%ori'm& /&imple or propo&ed i)i'iali>a'io)

al%ori'm are u&ed *or 'e &imula'io). Ta,le 3

'a,ula'e& 'e re&ul'& o* 'e &imula'io)& a)d 'e

&pe#i*i#a'io) o* ea# model. I) 'i& 'a,le( 'e

ee#u'io) 'ime&( 'e )um,er o* i))er a)d ou'er

loop #al#ula'io)&( 'e )um,er o* Ja#o,ea) ma'ri #ompu'a'io)( a)d 'e )um,er o* -E<D

*u)#'io) evalua'io)& are repor'ed.

Tale 1+ Specifications of the in!estigated ),ample 1-

.istillate rate/00 #mols 5eflu, ratio/12 and

$umer of trays/24

6eed

specs

Tray

numer

6lo& rate

#mols

Composition n( C 4 7 1 0

n( C 8 7 1 2

n( C 9 7 1 4

n( C : 7 1 9

Feed 1 ! 200.0 0.40 0.30 0.20 0.10Feed 2 1 200.0 0.05 0.25 0.30 0.40

Side product specsTray

numer

6lo& rate

#molsPhase

<ide produ#' 1 11 90 ;iCuid

<ide produ#' 2 18 110 apor

Te #olum) pre&&ure& are #o)&'a)' a' 1 a'mG all 'e

*eed& are #o)&idered 'o ,e a' ,u,,le poi)' 'emper

a'ure a' 1 a'm.

Te &imula'io) re&ul'& o* Ta,le 3 *or Eample 1

&o? 'a' 'e propo&ed i)i'iali>a'io) al%ori'm#a) redu#e 'e #ompu'a'io)al e**or' a)d &imula

'io) 'ime &i%)i*i#a)'l. Te #ompari&o) o* 'e

&imula'io) re&ul'& o* model& 1 a)d 3 ?i'

model& 2 a)d 4 reveal 'a' 'e propo&ed

i)i'iali>a'io) al%ori'm #a) improve 'e &imula

'io) pro#edure re%ardle&& o* 'e &ele#'ed damp

i)% me'od. Do?ever( i' i& o,viou& 'a' 'e

ou)di)% me'od provide& ,e''er dampi)%

pro#edure i) di&'illa'io) #olum) &imula'io) ?i'

&or'er &imula'io) 'ime.

8/11/2019 Jpst 2014 Vol. 4 No. 1






42 '

Tale 2+ Specifications of the in!estigated ),ample 2-

.istillate rate/1200 #mols 5eflu, ratio/40 and

$umer of trays/40

6eed

specs

Tray

numer

6lo&

rate#mols

Composition

i ( C 4 7 1 0

n( C 4 7 1 0

i ( C 8 7 1 2

n( C 8 7 1 2

n( C 9 7 1 4

Feed 1 10 200.0 0.!0 0.20 0.0! 0.03 0.00

Feed 2 30 200.0 0.03 0.0! 0.40 0.35 0.15

Side product specsTray

numer

6lo& rate

#molsPhase

<ide produ#' 1 20 10.0 apor

Te #olum) pre&&ure& are #o)&'a)' a' 1 a'mG all 'e

*eed& are #o)&idered 'o ,e a' ,u,,le poi)' 'emper

a'ure a' 1 a'm.

I) Fi%ure 1( 'e e&'ima'ed 'empera'ure a)d

rela'ive vola'ili' /)u'a)e 'o )e)'a)e

pro*ile& re&ul'ed *rom ,o' 'e i)ve&'i%a'ed

i)i'iali>a'io) al%ori'm& are #ompared ?i' 'e

*i)al ri%orou& &imula'io) re&ul'& o* i)&ideou'

al%ori'm. $& #a) ,e &ee) i) 'i& *i%ure( 'e

propo&ed i)i'iali>a'io) me'od provide& pro*ile&

#lo&er 'o 'e ri%orou& re&ul'&. Ti& #lo&er

e&'ima'io) ?ill re&ul' i) more a##ura'el ap

proima'ed 'ermod)ami# eCua'io)& a)d

'ere*ore a *e?er )um,er o* ou'er loop

i'era'io)&. Te e&'ima'ed value& are #lo&er 'o

'e 'rue value& a' 'e i)'ermedia'e 'ra&(

,e#au&e a' 'e&e lo#a'io)& 'e varia,le value&

are dire#'l #al#ula'ed , 'e approima'ed

&imula'io) me'od. Tu& dividi)% 'e #olum)

i)'o a lar%er )um,er o* &e#'io)& #a) improve 'e

Cuali' o* 'e i)i'ial e&'ima'io) o* #olum)

pro*ile&. Do?ever( 'i& o,viou&l re&ul'& i)*ur'er #ompu'a'io)&( ?i# are )o' u&uall

reCuired ,e#au&e 'e e&'ima'ed pro*ile& are )o'

)e#e&&ar 'o ,e ver a##ura'e. Do?ever( ?e)

'e )um,er o* &'a%e& i) o)e &e#'io) i& ver i%(

dividi)% i' i)'o a )um,er o* &u,&e#'io)& #a) ,e

,e)e*i#ial a)d #au&e &i%)i*i#a)' improveme)' i)

'e e&'ima'io) o* #olum) pro*ile&.

Eample 2 o* Ta,le 2 i)di#a'e& a di&'illa'io)

#olum) ?i' '?o *eed a)d 'ree produ#'&. $&

#a) ,e &ee) i) Ta,le 3( o)l 'ree model& #a)

&imula'e 'i& #olum) a)d 'e model ?i' &imple

i)i'iali>a'io) al%ori'm a)d rode) dampi)%

me'od #a))o' &u##e&&*ull #o)ver%e.

6igure 1+ Comparison of estimated column profiles

from the simple and proposed initiali;ation

methods &ith respect to the rigorous simulation

results for ),ample 1

Fi%ure 2 i)di#a'e& 'e 'empera'ure pro*ile

e&'ima'io)& *rom '?o i)ve&'i%a'ed i)i'iali>a'io)

al%ori'm& a)d #ompare& 'em ?i' 'e

ri%orou& &imula'io) re&ul'&. I) 'i& eample( 'edi**ere)#e& ,e'?ee) 'e re&ul'& o* 'e &imple

i)i'iali>a'io) me'od a)d *i)al ri%orou& re&ul'&

are more #o)&idera,le. Tere*ore( ver lar%e

#a)%e& are reCuired i) i))er loop varia,le&.

rode)A& dampi)% me'od #oo&e& a dampi)%

*a#'or 'o de#rea&e 'e &um o* -E<DA& di&#rep

a)# *u)#'io)& re%ardle&& o* 'e evalua'ed

#a)%e& ma%)i'ude.

2!0

290

310

330

350

3!0

0 5 10 15 20 25

T e m p e r a t u r e 1 % 3

Tray $um*er

ropo&ed -e'od

<imple -e'od

"i%orou& -e'od

2.5

3

3.5

4

4.5

0 5 10 15 20 25

5 e l a t i ! e < o l a t i l i t y 1 C

4 2 C 8

3

Tray $um*er

ropo&ed -e'od

<imple -e'od

"i%orou& -e'od

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Journal of Petroleum6evelopi)% a e? I)i'iali>a'io) ro#edure Science and Technology



' 43

Tale 3+ Simulation results of the four in!estigated models

),ample 1 ),ample 2

=odel"nitiali;ation

algorithm

.amping

factor

method

> u t e r l o o p

" n n e r l o o p

J a c o * e a n

=) S

7

T i m e

s 3

> u t e r l o o p

" n n e r l o o p

J a c o * e a n

=) S

7

T i m e

s 3

-odel 1 ropo&ed ou)di)% 2 8 2 2 0.098 2 21 2 105 0.203

-odel 2 <imple ou)di)% 3 20 3 101 0.144 4 58 4 22 0.401

-odel 3 ropo&ed rode) 2 25 4 133 0.130 2 4! 4 215 0.281

-odel 4 <imple rode) 3 4! 211 0.189 K

K: o' o)ver%e

Le) 'e&e #al#ula'ed #a)%e& are ver i%(

'i& dampi)% pro#edure re&ul'& i) )e? i))er

loop varia,le& 'a' ma ,e impo&&i,le i)di&'illa'io) #olum)&. I) 'e&e &i'ua'io)&(

,ou)di)% me'od #oo&e& a dampi)% *a#'or 'a'

i& re&'ri#'ed , 'e maimum allo?a,le #a)%e&

i) 'e i))er loop varia,le& a)d 'ere*ore re&ul'&

i) )e? po&&i,le i))er loop varia,le&. Ti& *a#' i&

'e mai) rea&o) *or 'e #o)ver%e)#e o* -odel 2

i) 'i& eample.

6igure 2+ )stimated temperature profiles from

simple initiali;ation proposed initiali;ation and

rigorous simulation for ),ample 2

Le) 'e i)i'ial e&'ima'e& are #lo&er 'o 'e 'rue

varia,le&( &maller #a)%e& are #o)&eCue)'l

reCuired. Tere*ore( 'e reCuired #a)%e& 'o

mi)imi>e 'e &um o* di&#repa)# *u)#'io)&

/#ompu'ed , rode)A& me'od are i) a)

a##ep'a,le ra)%e a)d 'e &imula'io) model #a)

eve)'uall #o)ver%e. Te propo&ed i)i'iali>a'io)

al%ori'm #a) lead 'o #o)ver%e)#e ,

i)'rodu#i)% 'e&e ,e''er e&'ima'i)% value&.

$l'ou% 'e re&ul'ed 'ime &avi)% , 'e

propo&ed i)i'iali>a'io) al%ori'm i& )o' ver

impor'a)' *or &i)%le &imula'io) pro,lem&( ?e)

a lar%e )um,er o* &imula'io) ru)& mu&' ,e

per*ormed 'o *i)d 'e op'imum #o)di'io)( i' i& a

#o)&idera,le value. 6i&'illa'io) #olum) &eCue)#

i)%( pro#e&& &)'e&i& pro,lem&( a)d 'e

op'imi>a'io) o* di&'illa'io) #olum) #o)di'io)&

are 'e ?ellk)o?) eample& o* 'e&e pro,lem&.

Fur'ermore( 'e propo&ed al%ori'm #a)

improve 'e #o)ver%e)#e po&&i,ili'( ?i# i&e&&e)'ial i) all 'e &imula'io) model&.

Fur'ermore( Fi%ure& 1 a)d 2 &o? 'a' 'e

propo&ed me'od #a) ,e u&ed a& a) appro

ima'i)% &imula'io) me'od *or de'ermi)i)% 'e

produ#' #ompo&i'io)& o* &imple a)d #omple

di&'illa'io) #olum)& ,a&ed o) 'e mai) '?o

a&&ump'io)&( )amel #o)&'a)' molar over*lo?

a)d #o)&'a)' rela'ive vola'ili'.

CONCLUSIONS

o)ver%e)#e a)d &peed are '?o impor'a)'

*a#'or& i) di&'illa'io) #olum) &imula'io)&. Te

propo&ed i)i'iali>a'io) al%ori'm #a) &i%)i*

#a)'l improve ,o' *a#'or& ?i' e&'ima'i)%

more a##ura'e #olum) pro*ile&. Ti& a##ura#

#a) ,e o,'ai)ed ?i' )e%li%i,le #ompu'a'io)al

e**or' ,a&ed o) 'e approima'ed &imula'io)

pro#edure. Tere*ore( i' i& #o)ve)ie)' 'o repla#e

'e &imple 'radi'io)al i)i'iali>a'io) me'od ?i'

20

2!5

290

305

320

0 10 20 30 40

T e m p e r a t u r e 1 % 3

Tray $um*er

ropo&ed -e'od

<imple -e'od"i%orou& -e'od

8/11/2019 Jpst 2014 Vol. 4 No. 1






44 '

'e propo&ed me'od.

NOMENCLATURE

Are!iations

= e)'ral pro#e&&i)% u)i'-E<D

ECua'io)&

-a'erial ,ala)#e /-a&e

ECuili,rium /Emole *ra#'io)

<umma'io) /<E)er%

,ala)#e /D eCua'io)&

REFERENCES

1 i&'er D. M.( Distillation Design( ap'er 4(

e? Nork: -#Ora?Dill( 12( 135.

2 Jai)a <.( <mi'a( ".( a)d im( J. .(

P<)'e&i& o* Dea'i)'e%ra'ed 6i&'illa'io)<eCue)#e <&'em&(Q Journal of the Taiwan

Institute of Chemical Engineers( 2012( 43(

525534.

3 $di#e . a)d o%elpol( $l.( P<or'#u'

-e'od& *or 'e 7p'imal 6e&i%) o* <imple

a)d omple 6i&'illa'io) olum)&(Q

Chemical Engineering Research and De

sign( 2011( !"( 13211332.

4 <eader J. 6. a)d De)le E. J.( Se#aration

Process Princi#les, e? Nork: Jo) Lile

a)d <o)&( 1?( 59.

5 Ivakpour J. a)d . a&iri( P6evelopme)' o*

a e? -odel *or 'e 6e'ermi)a'io) o*

7p'imum 6i&'illa'io) olum) <eCue)#e

*or o)&arp <epara'io)&(Q Ph$D$ Thesis(

Ira) =)iver&i' o* <#ie)#e a)d Te#)olo%(

Tera)( Ira)( 200.

Ivakpour J. a)d . a&iri.( PImprove <peed

a)d o)ver%e)#e o* 6i&'illa'io) olum)

<imula'io)(Q %ydrocar&on Process( 200?

!' ( 10( !580.

! rode) . O.( P$ la&& o* -e'od& *or

<olvi)% o)li)ear <imul'a)eou& ECua

'io)&(Q (athematics of Com#utation(

198( )"( 5!!593.

8/11/2019 Jpst 2014 Vol. 4 No. 1




Sina Shaddel


Tel: +98 912 404 5468

Fa: +98 21 8800 2622

Article history

!ecei"ed: #anuar$ 09% 201&

!ecei"ed in re"ised '(rm: #ul$ 21% 201&

)cce*ted: )uust 1,% 201&

)"aila-le (nline: arch 10% 2014

Journal of Petroleum Science and Technology 2014 , 4/1% 4554 htt*:3*st.ri*i.ir

2014 !esearch nstitute (' etr(leum ndustr$ /!

45

CORE FLOOD STUDIES TO EVALUATE EFFICIENCY OF OIL

RECOVERY BY LOW SALINITY WATER FLOODING AS A

SECONDARY RECOVERY PROCESS

Sina Shaddel1* !ahmoud "emmati

2 #hsan $amanian

% and &a'id &e(ati !oharrami

4

1 Sahand etr(leum !esearch 7enter% Sahand ni"ersit$ (' Techn(l($% Ta-ri% ran

2 !esearch nstitute (' etr(leum ndustr$ /!% Tehran% ran

& )mira-ir ni"ersit$ (' Techn(l($% Tehran% ran

4 Eshrah ni"ersit$% ;(3n(rd% ran

ABSTRACT

<ari(us researches (n la-(rat(r$ and 'ield scale illustrate that mani*ulatin the i(nic c(m*(siti(n

and the i(n c(ncentrati(n (' in3ected =ater can a''ect the e''icienc$ (' =ater 'l((din and the

interacti(n (' in3ected =ater =ith r(c and (ther 'luids *resent in *(r(us media. The (-3ecti"es ('

this *a*er are t( in"estiate *arameters that a''ect l(= salinit$ =ater 'l((din> mainl$ the e''ect ('

in3ectin =ater salinit$ (n and the *(tential (' l(= salinit$ =ater 'l((din '(r (il rec("er$ in

sec(ndar$ rec("er$ m(de are studied. The e''ect (' *? and di''erential *ressure acr(ss the c(re are

used t( e*lain the mechanism (' 'ine mirati(n *hen(mena. The rec("er$ results (' '(rmati(n

=ater in3ecti(n =ere c(m*ared '(r the sea=ater% '(rmati(n =ater =ith a salinit$ (' 0.1 and 0.01%

and =hen di"alent i(ns =ere rem("ed 'r(m the '(rmati(n =ater =ith a salinit$ (' 0.01 t(

in"estiate the e''ect (' di"alent i(ns (n (il rec("er$. i''erent t$*es (' crude (il =ere used '(r

in"estiatin the e''ect crude (il *r(*erties (n (il rec("er$. Sea=ater in3ecti(n resulted in l(=est (il

rec("er$ (' 2.6A and the reducti(n (' =ater salinit$ (' '(rmati(n =ater 'r(m 0.1 t( 0.01 resulted in

an im*r("ement (' 4 and ,.,A in (il rec("er$ res*ecti"el$. !em("in di"alent i(ns 'r(m the

in3ected =ater decreased the im*r("in e''ect (' l(= salinit$ =ater 'l((din. n additi(n% -(th t$*es

(' crude (il res*(nded t( l(= salinit$ 'l((din and n( straiht c(rrelati(n =as seen -et=een acid

num-er and the im*r("in e''ect (' l(= salinit$ =ater 'l((din.

)eyords: B(= Salinit$% Cater Fl((din% 7(re Fl((d% Dil !ec("er$% Sec(ndar$ !ec("er$

INTRODUCTION

;$ n(=% =ater 'l((din has =idel$ -een a**lied

in the =(rld t( im*r("e (il rec("er$. t has -een

(-ser"ed that the in3ecti(n (' dilute -rine can

increase (il rec("er$ as c(m*ared t( hih

salinit$ =ater in3ecti(n. The stud$ (' "aria-les

that a''ect dis*lacement mechanisms has -een

the su-3ect (' research interest '(r se"eral

decades. )m(n the man$ identi'ied 'act(rs

that a''ect (il rec("er$ -$ =ater 'l((din% the

c(m*(siti(n (' in3ectin =ater has -een sh(=n

t( the m(st im*(rtant 'act(r -ecause it is the

(nl$ *arameter that can -e mani*ulated 1%2.

The c(nnate =ater c(m*(siti(n has a *red(m

inant e''ect (n the 'luid distri-uti(n in *(r(us

media and determines =etta-ilit$ states

induced -$ the ads(r*ti(n 'r(m crude (il &5.

Chen the c(nnate =ater has relati"el$ hih

8/11/2019 Jpst 2014 Vol. 4 No. 1



Science and Technology S. Shaddel% . ?emmati% E. Gamanian% and H. He3ati (harrami

Journal of Petroleum Science and Technology 2014% 4/1% 4554 htt*:3*st.ri*i.ir


4+ ,

salinit$% the in3ecti(n (' dilute -rine a"e

ec(n(micall$ sini'icant increase in (il rec("er$%

=hich ma$ -e -ecause (' miin =ith c(nnate

=ater and the creati(n (' a 'a"(ra-le c(nditi(n

'(r (il *r(ducti(n.

7rude (il t$*e and r(c t$*e /*articularl$ the

*resence and distri-uti(n (' cla$s -(th *la$ an

im*(rtant r(le in the e''ect that -rine chemistr$

has (n =ater 'l((din (il rec("er$. The crude

(il -riner(c interacti(ns that determine

dis*lacement e''icienc$ are hihl$ c(m*le 6%,.

Humer(us h$*(theses ha"e -een de"ised t(

e*lain the increase in (il *r(ducti(n ass(ciated

=ith l(= salinit$ =ater in3ecti(n% includinincreasin *? leadin t( in situ sa*(ni'icati(n

and inter'acial tensi(n reducti(n% emulsi(n '(r

mati(n% cla$ mirati(n% and =etta-ilit$ altera

ti(n 8%9.

) s(luti(n =ith l(=er salinit$ a''ects the

dis*ersi(n (' cla$ and silt in the '(rmati(n. The

cla$ and silt% u*(n dis*ersi(n% -ec(me m(-ile

and '(ll(= the *aths taen -$ the reatest

*r(*(rti(n (' the 'l(=in =ater. These *aths arethe d(mains (' hih *ermea-ilit$% and the

m(-ile cla$ and silt -ec(me l(ded in the

smaller *(re s*aces (' these d(mains and

reduce the 'l(= (' =ater thr(uh these *(re

s*aces. The *ermea-ilit$ (' the d(mains =here

cla$ and silt are l(ded is acc(rdinl$ reduced%

and the =ater is '(rced t( tae (ther 'l(= *aths.

)s a result% the *ermea-ilities in these d(mains

=ithin the '(rmati(n -ec(me m(re uni'(rm. )

reducti(n in *ermea-ilit$ in the m(re *ermea

-le d(mains im*r("es the m(-ilit$ rati( ('

=ater 'l((din. remature -reathr(uh is thus

reduced% and the e''icienc$ (' the =ater

'l((din is im*r("ed 10.

) *? increase is ass(ciated =ith dilute -rine

in3ecti(n in numer(us la-(rat(r$ tests. The *?

increase c(uld -e e*lained -$ car-(nate

diss(luti(n and cati(n echanes 11. urin

the diss(luti(n (' car-(nate% an ecess (' D?

i"es increased *?. 7ati(n echane (ccurs

-et=een cla$ minerals and the in"adin l(=

salinit$ -rine. )n echane (' ?+ in the liIuid

*hase =ith cati(ns *re"i(usl$ ads(r-ed at the

mineral sur'ace leads t( a decrease (' ?+

c(ncentrati(n inside the liIuid *hase. This c(uld

als( result in a *? increase.

ulti i(n echane is an(ther mechanism that

e*lains h(= l(= salinit$ =ater 'l((din

in'luences the (il rec("er$. ultic(m*(nent

i(n echane /E taes *lace -et=een

ads(r-ed crude (il c(m*(nents% the cla$

mineral sur'ace% and the cati(ns in the -rine%

=hen l(= salinit$ -rine% =hich c(ntains l(=

c(ncentrati(ns (' 2+

and 7a2+

% are in3ected.

i"alent cati(ns 'r(m the in3ected -rine

echane =ith either cati(nic (ranic c(m*lees

(r =ith -ases% due t( the chane in i(nic

eIuili-rium. The cla$ sur'ace -ec(mes m(re

=ater=et as a result (' the rem("al (' *(lar

(ranic c(m*(unds and (ran(metallic c(m

*lees 'r(m the cla$ sur'ace. This als( increases

the (il rec("er$.

n 2009% Bithelm et al. *r(*(sed the BS

mechanism t( -e the e*ansi(n (' the electrical

d(u-le la$ers that surr(und the cla$ and (il

*articles and increase in the le"el (' eta

*(tential 6. t =as suested that a decrease in

the i(nic strenth -$ l(=erin the salinit$ in the

-rine =(uld increase the electr(static re*ulsi(n

-et=een the cla$ *articles and the (il. Dnce the

re*ulsi"e '(rces eceed the -indin '(rces "ia

the multi"alent cati(n -rides% the (il *articlesma$ -e ads(r-ed 'r(m the cla$ sur'ace% =hich

leads t( a chane in =ettin *hase t(=ards

increased =ater =etness. ' the electr(l$te

c(ncentrati(n is 'urther reduced% the electr(

static '(rces =ithin the cla$ minerals starts t(

eceed -indin '(rces% =hich ma$ lead t(

'(rmati(n damae.

n this stud$% in additi(n t( (il rec("er$ data% the

*? (' aIue(us s(luti(n 'l(=in (ut 'r(m c(res

8/11/2019 Jpst 2014 Vol. 4 No. 1


Journal of Petroleum7(re Fl((d Studies t( E"aluate E''icienc$ J Science and Technology



, 4-

durin c(re 'l((d e*eriments =as studied t(

determine the ca*a-ilit$ (' i(n echane -e

t=een r(c and the in3ected =ater.

EXPERIMENTAL

Materials

Core !aterial: in this stud$% 'i"e reser"(ir c(re

sam*les =ith desinati(ns (' )1 t( )5 =ere

used. 7(re sam*les =ere (-tained 'r(m the

sandst(ne secti(n (' an (il reser"(ir in ran. The

*(r(sit$ and *ermea-ilit$ (' c(res =ere

measured usin c(re'l((d a**aratus and hih

salinit$ '(rmati(n -rine% Ta-les 1 and 2 sh(= the

mineral($ and r(c *r(*erties (' c(re *lus

res*ecti"el$. The *(r(sit$ and *ermea-ilit$

ranes =ere 1419 <(l.A and 42, m res*ect

ti"el$. )s it can -e seen in Ta-le 2% the c(re

*lus )1 and )5 ha"e di''erent *(r(sit$ and

*ermea-ilit$ =ith res*ect t( the (ther *lus. n

this stud$% the reser"(ir c(res =ere used and the

(al =as t( (-tain the maimum num-er ('

*lus. These t=( c(res =ere (-tained in

di''erent directi(ns =ith res*ect t( the (ther

*lus and there'(re had di''erent *r(*erties.The main c(ncern =as that all the c(res had the

same mineral($ t( ena-le the c(m*aris(n ('

results.

Ta.le 1/ !ineralogy of sandstone cores *t3

!usco'ite)aoliniteolomiteCalciteAl.iteuart6

2424216,

7luids: all the -rines =ere *re*ared in the

la-(rat(r$ -$ res(l"in reaent rade salts in

dei(nied =ater. Ta-le & ta-ulates the

c(m*(siti(n (' '(rmati(n -rine and sea =ater.

B(= salinit$ =ater =as made -$ dilutin the

'(rmati(n =ater t( salinit$ (' 0.1 and 0.01. n

(ne e*eriment% di"alent i(ns =ere rem("ed

'r(m the in3ected =ater t( in"estiate the e''ect

(' di"alent i(ns (n (il rec("er$.

Ta.le %/ Composition of formation *ater and

sea *ater

Sea 8ater

mg9l3

7ormation 8ater

mg9l3Components

12,6&6&204Ha+ and K

+

&821&6007a2+

142426,&2+

2212012,4&67l

&118500SD42

&980,20,41&TS /**m

Crude oil: t=( t$*es (' crude (ils =ere used '(r

saturatin the c(res% crude A and crude B.

Filtered st(c tan crude (ils =ere used '(r

ain the c(re sam*les. Ta-le 4 lists s(me

*r(*erties (' the (il at r((m tem*erature. The

acid num-er (' crude (il =as measured in the

la-(rat(r$ acc(rdin t( m(di'ied )ST 664

meth(d.

Ta.le 4/ Properties of crude oils

A&9:& mg

);"9g oil3<iscosity cp3ensity g9cm

%3

;il

Sample

0.8420.21&.150.8549Crude A

1.68&0.424.2,0.920&Crude B

Ta.le 2/ =oc> properties of core plugs

Aging Time ay3Si 3Permea.ility m3Porosity 3iameter m3?ength m3Core @

20&0.,14.&515.6&0.0&,90.05A1

2029.120.9814.620.0&80.0484A2

20&1.42,.1114.910.0&80.049A%

20&1.22&.,016.80.0&80.0491A4

20&2.1&.9419.410.0&80.049A5

8/11/2019 Jpst 2014 Vol. 4 No. 1






4 ,

Core Preparation

Core cleaning: the c(res =ere cleaned -$

S(hlet etracti(n usin t(luene and methan(l%

and then dried at 100 L7. )'ter dr$in% the c(re

dimensi(ns% =eiht% and *ermea-ilit$ =ere

measured.

:rine saturation: the c(re sam*les =ere

saturated =ith '(rmati(n =ater. )'ter saturati(n

=as achie"ed% -ase *ermea-ilit$ =as then

measured at three di''erent 'l(= rates and

all(=ed 15 da$s at 50 L7 '(r i(nic eIuili-rium t(

-e esta-lished -et=een the r(c and the

'(rmati(n =ater. Ceiht meth(d =as a**lied t(

measure *(r(sit$.

#sta.lishment S wi : the initial =ater saturati(n

/Swi =as esta-lished -$ the in3ecti(n (' dead

crude (il int( the c(res until the irreduci-le

=ater saturati(n =as reached and n( m(re

=ater =as *r(duced 'r(m the eamined c(re.

The directi(n (' 'l(= =as re"ersed a'ter 2 *(re

"(lumes /< in3ecti(n (' crude (il t( i"e

uni'(rm saturati(n distri-uti(n al(n the c(re.

Aging: a'ter esta-lishin Swi -$ dis*lacement

=ith crude (il% the c(res =ere rem("ed 'r(m the

c(re h(lder and aed in crude (il in sealed $re

3ars. The cells =ere sealed and held at 90 L7 '(r

20 da$s.

=estoration of core: a'ter 'l((din the c(re =ith

di''erent -rines% in the cases =here rest(rati(n

=as needed% the c(re =as rest(red t( its initial

state -$ cleanin the c(re. The rest(rati(n =as

*er'(rmed a'ter 'irst 'l((din e*eriment -$'(rmati(n =ater '(r each c(re *lu. )'ter

rest(rati(n the c(re *lus t( initial state% the$

=ere read$ '(r l(= salinit$ =ater 'l((din

e*eriments. The rest(rati(n =as d(ne -$ the

same *r(cedure as descri-ed -e'(re.

Water flooding Tests

) c(reh(lder a**aratus =as used in the 'l((din

e*eriments. The c(re =as *laced in the

c(reh(lder =ith a c(n'inin *ressure (' 140 -ar

acc(rdin t( aial stress (' the de*th that c(re

*re*ared. dentical 'l((din c(nditi(ns i.e. a

tem*erature (' 50 L7% ra"it$ sta-le dis*lace

ment% and a n(minal 'l((din rate (' 2 <da$

=ere used in all the 'l((ds. Furtherm(re% a

-ac*ressure (' 5 -ars =as a**lied t( a"(id the

'(rmati(n (' as -$ liht ends in the crude (il.

The *ressure dr(* acr(ss the c(re =as care'ull$

m(nit(red in all the e*eriments. T=( 'l((ds

=ere *er'(rmed (n each c(re. The 'irst 'l((d

=as a c(ntinu(us in3ecti(n (' '(rmati(n =ater

/hih salinit$ -rine t( remainin (il saturati(n%

=hile the sec(nd 'l((d =as a l(= salinit$ =ater

in3ecti(n. !emainin (il saturati(n a'ter =ater

'l((din =as c(nsidered t( -e (-tained =hen

=ater cut "alues =ere hih and sta-le ("er time.

The *r(duced (il =as c(llected usin a 'racti(nal

c(llect(r and the (il rec("er$ =as determined as

the *ercentae (' (riinal (il in *lace /*ercent

ae (' DD. The e''luent sam*les =ere

c(llected reularl$ and *? =as measured and

rec(rded. Ta-le 5 sh(=s the e*erimental la$

(ut (' c(re dis*lacement e*eriments. Fiure 1

sh(=s the schematic (' c(re 'l((din set u* '(r

the e*eriments.

Ta.le 5/ #Bperimental layout of core displacement eBperiments at 50 C

Test Core @ 1st flood=eco'ery

;;@P3?S8 flood

=eco'ery

;;@P3Crude type

Test 1 )4 FC 48.2 SC 50.8 ;

Test 2 )& FC 50 0.1 FC 54 ;

Test & )2 FC 49 0.01 FC 56., ;

Test 4 )1 FC 51.5 0.01 FC /(nl$ m(n("alent i(ns 5,.5 ;

Test 5 )5 FC 49 0.01 FC 56 )

8/11/2019 Jpst 2014 Vol. 4 No. 1





, 4D

7igure 1/ A schematic of coreEflood set up

?o salinity ater flooding .y seaater: in this

e*eriment% sea=ater =as used '(r 'l((din in

c(re )4 t( c(m*are (il rec("er$ "alues =ith

th(se (-tained 'r(m '(rmati(n -rine in3ecti(n in

sec(ndar$ rec("er$ m(de. F(rmati(n =ater

in3ecti(n resulted in 48.2A (il rec("er$ ('

(riinal (il in *lace /DD and sea=ater

in3ecti(n *r(duced 50.8A (il rec("er$ (' (riinal

(il in *lace. The *? (' e''luent =ater =as in the

rane (' 6.25 t( 6.51 and 6.29 t( 6.62 '(r

'(rmati(n =ater and sea =ater in3ecti(ns

res*ecti"el$. Fiure 2 sh(=s the (il rec("er$

*r('iles% "ariati(n (' di''erential *ressures% and

the *? (' e''luent =ater =ith res*ect t( the

*(re "(lume in3ected.

?o salinity ater flooding .y 01 formation

ater: the in3ecti(n (' '(rmati(n =ater int(

c(re )& resulted in 50A (il rec("er$ (' (riinal

(il in *lace /DD and the *? (' e''luent =ater

in '(rmati(n =ater in3ecti(n =as in the rane ('

6.58 t( 6.84. Then% a'ter rest(rati(n% =ater =ith

salinit$ (' 0.1 '(rmati(n =ater resulted in 54A

(il rec("er$ (' (riinal (il in *lace and the *? ('

e''luent =ater =as -et=een 6.48 and 6.,. Dil

rec("er$% *ressure dr(*% and the *? (' e''luent

=ater are sh(=n in Fiure &.

7igure 2/ a3 pressure drop and .3 oil reco'ery and

p" e'olution during secondary reco'ery eBperiment

on A4

0

500

1000

1500

2000

2500

0 1 2 & 4 5

P 4 0 m . a

r 3

:rine P< @n(ected

a

6

,

8

9

0

20

40

60

80

0 1 2 & 4 5

p "

; i l = e c o ' e r y

7 a c t o r

0 2 ; ; @ P 3

:rine P< @n(ected

.SC !ec.

FC !ec.

?

8/11/2019 Jpst 2014 Vol. 4 No. 1






50 ,

7igure %/ a3 pressure drop and .3 oil reco'ery and


on A%

?o salinity ater flooding .y 001 formationater: '(rmati(n =ater in3ecti(n int( c(re )2

resulted in 49A (il rec("er$ (' (riinal (il in

*lace /DD and the *? (' e''luent =ater in

'(rmati(n =ater in3ecti(n =as in the rane ('

6.&2 t( 6.61. F(r in"estiatin the e''ect (' l(=

salinit$ 'l((din and reachin (*timum in3ecti(n

=ater salinit$% the '(rmati(n =ater =as diluted

t( salinit$ (' 0.01 '(rmati(n =ater% =hich

resulted in 56.,A (il rec("er$ (' (riinal (il in

*lace and the *? (' e''luent =ater =as in the

rane (' 6.5& t( 6.95. Fiure 4 sh(=s (il

rec("er$% *ressure dr(*% and the *? (' e''luent

=ater thr(uh the c(re "ersus the in3ected *(re

"(lume.


ater ith only mono'alent ions: c(re )1 =as

'l((ded =ith a '(rmati(n =ater and the

rec("er$ 'act(r =as 51.5A rec("er$ (' (riinal

(il in *lace /DD> the in3ecti(n (' =ater =ith

salinit$ (' 0.01 '(rmati(n =ater =hich c(ntains

(nl$ m(n("alent i(ns /Ha% K% and 7l =ith(ut 7a

and i(ns resulted in an (il rec("er$ 'act(r ('

5,.5A. The e''luent =ater *? '(r '(rmati(n

=ater in3ecti(n =as -et=een 6.2 and 6.,1 and in'urther 'l((din -et=een 5.9 and 6.92. Fiure 5

sh(=s the (il rec("er$ *r('iles% the "ariati(n ('

di''erential *ressures% and the *? (' e''luent

=ater =ith res*ect t( the *(re "(lume in3ected.



on A2


ater and crude type A: the c(re )5 =as

saturated =ith crude t$*e ) t( in"estiate the

e''ect (' the t$*e (' crude (il (n (il rec("er$>

the (ther c(nditi(ns =ere identical t( the (ther

e*eriments ece*t the t$*e (' crude (il. The

e*eriment =ith crude ) resulted in 51.5A (il

rec("er$ (' (riinal (il in *lace /DD and the

in3ecti(n (' l(= salinit$ =ater =ith salinit$ ('

0.01 '(rmati(n =ater lead t( an (il rec("er$ ('

0

200

400

600

800

0 1 2 & 4 5

P 4

0 m . a r 3

:rine P< @n(ected

a

6

,

8

9

0

20

40

60

80

0 1 2 & 4 5

p

"

; i l = e c o '

e r y 7 a c t o r

0 2 ;

; @ P 3

:rine P< @n(ected

.0.1FC !ec.

FC !ec.

?

0

500

1000

1500

2000

2500

&000

0 1 2 & 4 5

P 4 0 m . a r 3

:rine P< @n(ected

a

6

,

8

9

0

20

40

60

80

0 1 2 & 4 5

p "

; i l = e c o ' e

r y 7 a c t o r

0 2 ; ;

@ P 3

:rine P< @n(ected

.0.01FC !ec.

FC !ec.

?

8/11/2019 Jpst 2014 Vol. 4 No. 1





, 51

56A.



on A1

The *? (' e''luent =ater '(r '(rmati(n =aterin3ecti(n and the in3ecti(n (' =ater =ith salinit$

(' 0.01 '(rmati(n =ater =as in the rane (' 6.8

t( ,.22 and 6.2 t( ,.0& res*ecti"el$. Fiure 6

sh(=s (il rec("er$% *ressure dr(*% and the *? ('

e''luent =ater thr(uh the c(re "ersus the

in3ected *(re "(lume.


n this secti(n% the (-tained results are

anal$ed. The main *ur*(se (' stud$ =as the

eaminati(n (' the a-ilit$ (' l(= salinit$ =ater

in im*r("in (il rec("er$ in ranian sandst(ne in

sec(ndar$ rec("er$ m(de. ?erein% the results ('

'l((din 5 sandst(ne c(res =ere c(m*ared =ith

'(rmati(n =ater in3ecti(n int( them t(

in"estiate the e''ect (' l(= salinit$ =ater

'l((din (n (il rec("er$ in sec(ndar$ rec("er$

m(de. The selected c(res =ere =ell s(rted and

mainl$ c(m*(sed (' Iuart% al-ite% and trace

am(unts (' calcite and d(l(mite> the c(res had

s(me am(unts (' cla$s =hich =ere mainl$

a(linite and musc("ite. F(r decreasin the

=ater =etness (' c(res% an ain *eri(d (' 20

da$s at a tem*erature (' 90 L7 =as ch(sen.

7igure +/ a3 pressure drop and .3 oil reco'ery and


on A5

The rec("er$ data -$ '(rmati(n =ater in3ecti(n

'(r these c(res =ere (-tained 'r(m an(ther set

(' e*eriments. ?erein% the results (' l(=

salinit$ 'l((din (' c(res in sec(ndar$ m(de are

*resented and c(m*ared =ith '(rmati(n =ater

in3ecti(n data. ;ecause the c(res =ere used(nce '(r l(= salinit$ 'l((din in tertiar$ m(de%

=e -elie"e that inter*retati(n and c(m*aris(ns

-et=een c(res must -e treated =ith cauti(n in

the case (' seIuential 'l((din (n indi"idual

c(res. nteracti(ns -et=een r(c(il-rine ma$

result in identi'ia-le chanes in res*(nse 'r(m

(ne 'l((d t( the net. Humer(us h$*(theses

ha"e -een de"ised t( e*lain the increase in (il

*r(ducti(n ass(ciated =ith l(= salinit$ =ater

in3ecti(n> h(=e"er% the in"estiati(n (' the

0

1000

2000

&000

4000

5000

0 1 2 & 4 5

P 4 0 m

. a r 3

:rine P< @n(ected

a

6

,

8

9

0

20

40

60

80

0 1 2 & 4 5

p "

; i l = e c o ' e

r y 7 a c t o r

0 2 ; ; @ P 3

:rine P< @n(ected

.0.01FC/(n( !ec.

FC !ec.

*?0

1000

2000

&000

4000

5000

0 1 2 & 4 5

P 4 0 m . a r 3

:rine P< @n(ected

a

Crude A

6

,

8

9

0

20

40

60

80

0 1 2 & 4 5

p "

; i l = e c o ' e r y 7 a c t o r

0 2 ; ; @ P 3

:rine P< @n(ected

.0.01FC/7rude ) !ec.

FC !ec.

?

8/11/2019 Jpst 2014 Vol. 4 No. 1






52 ,

mechanisms -$ =hich rec("er$ is increased

*resents a c(nsidera-le challene -ecause the$

de*end (n c(m*le crude (il-riner(c

interacti(ns. These c(res had l(= cla$ c(ntent

a-(ut 6A and limited 'ine mirati(n =as(-ser"ed in sam*lin tu-es> there'(re% =e thin

that this im*r("in e''ect in (il rec("er$ is a

result (' multic(m*(nent i(n echane -et

=een the in3ected l(= salinit$ -rine and r(c

sur'ace% =hich causes a reducti(n in i(n -indin

-et=een the crude (il and the r(c sur'ace t( -e

the main reas(n '(r increasin (il rec("er$ -$

l(= salinit$ =ater. ulti"alent cati(ns at cla$

sur'aces are -(nded t( *(lar c(m*(unds

*resent in the (il *hase /resin and as*haltene

'(rmin (ran(metallic c(m*lees and *r(

m(tin (il=etness (n r(c sur'aces.

ean=hile% s(me (ranic *(lar c(m*(unds are

directl$ ads(r-ed (nt( the mineral sur'ace%

dis*lacin the m(st la-ile cati(ns *resent at the

cla$ sur'ace and enhancin the (il=etness ('

the cla$ sur'ace. urin the in3ecti(n (' l(=

salinit$ -rine% E taes *lace% =hich rem("es

(ranic *(lar c(m*(unds and (ran(metallicc(m*lees 'r(m the sur'ace and re*laces them

=ith unc(m*leed cati(ns 9.

t is enerall$ acce*ted that the ads(r*ti(n ('

*(lar c(m*(unds (nt( r(c sur'ace has a

sini'icant e''ect (n the =etta-ilit$ (' reser"(irs

1119. T( esta-lish a =ide rane (' the initial

=ettin c(nditi(ns% t=( t$*es (' crude (ils =ith

di''erent c(ncentrati(ns (' *(lar c(m*(nents%

)H and ;H% =ere used. The "ariati(n (' aintime (' a c(re in crude (il is a "ia-le *arameter

'(r (-tainin s$stematic chanes in =etta-ilit$.

n this stud$% t=( t$*es (' crude (ils =ith

di''erent c(ncentrati(ns (' *(lar c(m*(nents%

)H and ;H% =ere used% namel$ (il ) =ith )H and

;H (' 0.842 /m (' KD? and 0.21 /m ('

KD? res*ecti"el$ and (il ; =ith )H and ;H ('

1.68& and 0.42 /m (' KD?.

The crude (il desinated ) has a l(=er acid

num-er and is used '(r the in"estiati(n (' the

e''ect (' crude (il (n l(= salinit$ =ater 'l((din.

The di''erence -et=een rec("eries (' the t=(

t$*es (' crude (il can -e -ecause (' l(=er acid

num-er (' crude )> h(=e"er% (ther e''ecti"e*arameters must -e sur"e$ed and (ur h$*(

thesis is n(t c(m*lete -ecause the drastic

mechanism is a c(nseIuence (' man$ *arame

ters and the interacti(n (' r(c(il-rine =hich

is c(m*le

The instantane(us *ermea-ilit$ "ersus the *(re

"(lume (' in3ectin =ater is sh(=n in Fiure ,.

The in"estiati(n (' this ra*h c(uld hel* the

e*lanati(n (' *r(-a-le 'ine mirati(n *hen(m

ena. !educin the in3ectin =ater salinit$ ma$

cause 'ine m("ement in *(r(us media. The

reducti(n (' *ermea-ilit$ in each ste* is an

indicati(n (' 'ine mirati(n and -l(cae (' *(re

thr(ats.

7igure -/ <ariation of instantaneous permea.ility 's

the pore 'olume in(ected

The tas t( tae int( acc(unt the (ut*ut (' the

l(= salinit$ =ater D!e''ect is n(t straiht

'(r=ard as the in'luence (' ende''ect ma$

induce s(me derees (' uncertaint$ in the

measurements (' additi(nal (il rec("er$. The

measurement (' small dr(*lets (' (il at the end

ste*s (' (il *r(ducti(n 'r(m c(re =(uld cause

s(me uncertaint$% since '(r accurate measure

ment% se"eral re'erence tu-es =ith n(=n

"(lumes (' (il and '(rmati(n =ater =ere used.

0.5

0.6

0.,

0.8

0.9

1.0

0 1 2 & 4 5

K f i n a l

/ K i n i t i a l

P< @n(ected

Dnl$ (n.<.(ns

0.01FC

0.1FC

SC

7rude )

8/11/2019 Jpst 2014 Vol. 4 No. 1





, 5%

The t(lerance in measurin the e''luent *? and

di''erential *ressure =as M0.05 unit and M0.001

m-ar res*ecti"el$.

CONCLUSIONS

1 H(t all le"els (' l(= salinit$ can increase the

(il rec("er$ in sandst(ne reser"(irs. )n

(*timum salinit$ le"el sh(uld n(t -e

eceeded t( rec("er m(re (il. The chemistr$

(' the in3ecti(n =ater is "er$ im*(rtant and

it sh(=s a sini'icant im*act (n (il rec("er$.

2 The etent (' the increase in (il rec("er$ -$

l(= salinit$ =ater 'l((din is hihl$ s*eci'ic

t( crude (il-riner(c /7D;! interacti(ns

and cann(t -e *redicted.&

The l(= salinit$ =ater sh(=s the *(tential

'(r im*r("in (il rec("er$ in sec(ndar$

m(de '(r these sandst(ne c(res.

4 The increase in e''luent =ater *? =as n(t

hih and the maimum increase in *? =as

in the case (' usin crude t$*e ) and eIual

t( 1 unit.

5 The maimum im*r("in e''ect (' usin l(=

salinit$ =ater =as in the case (' usin crude

t$*e ; and the in3ecti(n (' 0.01 '(rmati(n

=ater% =hich im*r("ed the sec(ndar$

rec("er$ -$ an additi(nal (il rec("er$ ('

,.,A (' (riinal (il in *lace /DD.

6

Nains (' rec("er$ =ere mainl$ (ccurred in

the 'irst three *(re "(lumes and =ere n(t

acc(m*anied -$ a sini'icant *? increase>

h(=e"er% *ressure dr(* increased. The

increase c(uld als( (ccur =ith(ut additi(nal

(il *r(ducti(n.,

n c(nclusi(n% increasin *? (r 'ine material

mirati(n =ere n(t seen durin (ur stud$

-ut =e c(n3ecture that cati(n echane

-et=een the mineral sur'ace and the

in"adin -rine is the *rimar$ mechanism

underl$in the im*r("ed =ater 'l((din

rec("er$ (-ser"ed =ith l(= salinit$ =ater

'l((din.

NOMENCLATURE

)H )cid num-er

;H ;ase num-er

i''erential *ressure

FC F(rmati(n =ater

denti'icati(n

B.S.C. B(= salinit$ =ater

m illidarc$

E ultic(m*(nent (n Echane

DD Driinal (il in *lace

ressure dr(*

< (re "(lume

Swi nitial =ater saturati(n

SC Sea =ater

TS T(tal diss(l"ed s(lid

REFERENCES

1 B(ahard3( H.% Oie O.% Pin .% and (rr(=

H. !.% QB(= Salinit$ Cater 'l((din (' )

!eser"(ir !(c%R a*er S7)200,29

*resentated at the International Sympo-

sium of the Society of Core Analysts,

7alar$% 7anada Se*tem-er 1012% 200-.

2 )ustad T.% !eaei (ust ).% and

unter"(ld T.% Q7hemical echanism ('

B(= Salinit$ Cater Fl((din in Sandst(ne

!eser"(irs%R a*er SE 129,6,. *res

ented at the 2! SP" Impro#ed $il

%eco#ery Symposium, Tulsa% Dlah(ma%

S)% )*ril 2428% 2010.

& Salathiel !. ).% QDil !ec("er$ -$ Sur'ace

Film rainae in ied Cetta-ilit$

!(cs%R J& Petrol& Technol&% 1D-%% 2'% 1216

1224.

4 #adhunandan . and (rr(= H. !.% QE''ect

(' Cetta-ilit$ (n Cater 'l((din !ec("er$'(r 7rude Dil;rine!(c S$stems ,( SP"

%eser#oir "ngineering% 1DD5% ! /1% 4046.

5

T(n G. O.% (rr(=% H. !.% Oie O.%

QS*(ntane(us m-i-iti(n '(r ied=ett

a-ilit$ States in Sandst(nes nduced -$

)ds(r*ti(n 'r(m 7rude Dil%R in *r(c. )th

International Symposium on %eser#oir

*etta+ility % )ustralia% 2002.

6

Bithelm . #.% Nr(ns"eld #.% ?('man #. .%

;russee H. #.% et al% QH("el Cater 'l((din

Strate$ -$ ani*ulati(n (' n3ecti(n

8/11/2019 Jpst 2014 Vol. 4 No. 1






54 ,

;rine 7(m*(siti(n%R a*er SE 1198&5.

*resented at the 2 SP" "%$P"C.

"A/" Annual Conference and "0hi+ition,

)msterdam% The Hetherlands% #une 811%

200D.

,

!eaei (ust ).% unter"(ld T.% and

)ustad T.% Q) iscussi(n (' the B(=

Salinit$ ED! (tential '(r a H(rth Sea

Sandst(ne Field%R a*er SE 1&4459.

resented at the SP" Annual Technical

Conference and "0hi+ition% Fl(rence% tal$%

Se*tem-er 1922% 2010.

8 )l(tai-i . ;.% )m$ !. .% and HasrEl

in ?. ).% Q) 7(m*rehensi"e ED! Stud$

sin B(= Salinit$ Cater in Sandst(ne

!eser"(irs%R a*er SE 1299,6. resentedat the 2! SP" Impro#ed $il %eco#ery

Symposium% Tulsa% Dlah(ma% S)% )*ril

2428% 2010.

9 Baer ).% Ce-- K. #.% ;lac 7. #. #.%

Sinlet(n .% et al.% QB(= Salinit$ Dil

!ec("er$: )n E*erimental n"estiati(n%R

a*er S7)2006&6. *resented at the

International Symposium of the Society of

Core Analysts Tr(ndheim% H(r=a$% Se*

tem-er 1216% 200+.

10

;(st(n C. N.% ;randner 7. F.% F(ster C. !.%Q!ec("er$ (' Dil -$ Cater 'l((din 'r(m

an )rillace(us% Dilc(ntainin Su-terra

nean F(rmati(n%R S atent & ,40 956%

Dct(-er 1D+D.

11 Tie% ?. and (rr(=% H.% QB(=Fl((d!ate

!esidual Saturati(n in 7ar-(nate !(cs%R

a*er SE 104,0 *resented at the SP"

International Petroleum Technology Con-

ference% (ha% H("em-er 212&% 2005.

12 (rr(=% H. !.% QCetta-ilit$ and its E''ect

(n Dil !ec("er$%R Journal of Petroleum

Technology % 1DD0% 12 /12 14,61484.

1& )nders(n C. N.% QCetta-ilit$ Biterature

Sur"e$art 2: Cetta-ilit$ easurement%R

Journal of Petroleum Technology % 1D+%

3% 12461262.

14 adsen B.% Nrahladsen B.% Nrn 7.% Bind

da% and Enell #.% Q)ds(r*ti(n (' (lar

)r(matic ?$dr(car-(ns (n S$nthetic

7alcite%R $rg& /eochemisrty % 1DD+% 21

/12% 11511155.

15

Th(mas . .% 7l(use #. ).% and B(n( #.

.% Q)ds(r*ti(n (' Dranic 7(m*(unds

(n 7ar-(nate inerals: 1. (del 7(m

*(unds and Their n'luence (n ineral

Cetta-ilit$%R Chemical /eology % 1DD%%

!% 20121&.

16

G(u B.% ?an ;.% Pan ?.% Kas*ersi K. B.% OuP.% and ?e*ler B. N.% QEnthal*$ (' )ds(r*

ti(n and s(therms '(r )ds(r*ti(n ('

Ha*hthenic )cid (nt( 7la$s%R J& Colloid 4

Interface Science% 1DD-% !% 4,24,5.

1,

Beens% 7.% T(ulh(at% ?.% 7uiec% B.%

<illieras% F.% and alerm(% T. QCetta-ilit$

7hane !elated t( the )ds(r*ti(n ('

Dranic )cids (n 7alcite: E*erimental

and )- niti( 7(m*utati(nal Studies%R

a*er SE 49&19 *resented at the SP"

Annual Technical Conference and "0hi+i-tion% He= Drleans% S)% Se*tem-er 2,&0%

1DD.

18 Ghan% . and )ustad% T. QThe !elati"e

E''ects (' )cid Hum-er and Tem*erature

(n 7hal Cetta-ilit$%R a*er SE 92999

*resented at the SP" International Sympo-

sium on $ilfield Chemistry % ?(ust(n% S)%

Fe-ruar$ 24% 2005.

8/11/2019 Jpst 2014 Vol. 4 No. 1




Alimorad Rashidi


Tel: +98 21 4825 2410

Fax:+98 21 4825 7676

Article history

Reei!ed: April 17" 2012

Reei!ed i# re!ised $orm: %&#e 12" 201'

Aep(ed: %&l) 1'" 201'

A!aila*le o#li#e: arh 10" 2014

Journal of Petroleum Science and Technology 2014 , 4,1-" 5560 h((p://ps(.ripi.ir

2014 Researh #s(i(&(e o$ 3e(role&m #d&s(r) ,R3-

55

A RIGOROUS COMPARISON OF METHODS FOR MULTI-WALLED

CARBON NANOTUBES PURIFICATION USING RAMAN

SPECTROSCOPY

oghayyeh !otfi" Alimorad ashidi*" and #ah$oo$eh #ohsennia

a#o(eh#olo) Researh e#(er" Researh #s(i(&(e o$ 3e(role&m #d&s(r) ,R3-" es( l!d. o$ Aadi por(s

omplex" Tehra#" 3.;. ox 146651998" ra#

ABSTRACT

&l(i<alled ar*o# #a#o(&*es ,T=s- <ere s)#(hesied &si# hemial !apor deposi(io# ,>?-

me(hod i# a $l&idied *ed rea(or &#der (he $lo< o$ me(ha#e a#d h)droe# ases. A o*al(

mol)*de#&m/ma#esi&m oxide ,oo/;- #a#oa(al)s( <as &sed as (he a(al)s( o$ (he proess.The samples <ere a#al)ed &si# sa##i# ele(ro# mirosop) ,E- a#d ra) di$$ra(io# ,R?-

a#al)ses. The e$$e(s o$ di$$ere#( om*i#a(io#s o$ p&ri$ia(io# me(hods" i#l&di# oxida(io#" l

(rea(me#(" a#d ;' (rea(me#( a#d (he seB&e#e o$ per$ormi# (hese me(hods o# (he B&ali() o$

(he ar*o# #a#o(&*es are dis&ssed. Rama# spe(rosop) <i(h a laser exi(a(io# o$ 5'2 #m <as

&(ilied as (he meas&reme#( (ool. The res&l(s pro!ide (he *es( p&ri$ia(io# me(hods o$ s)#(hesied

ar*o# #a#o(&*es. The IG/ID ra(io $or (he op(im&m sample is eB&al (o 1.28. oreo!er" as a#o(her

applia(io# o$ Rama# a#al)sis res&l(s" (he appare#( Co&#=s mod&l&s o$ T=s <as al&la(ed *)

(he &se o$ i#(e#si() ra(io ID/IG. As expe(ed" (he op(im&m sample had (he hihes( appare#( Co&#=s

mod&l&s o$ 40459.85 3a.

%ey&ords: &l(i<alled ar*o# a#o(&*es" 3&ri$ia(io#" hemial >apor ?eposi(io#" Rama#

pe(rosop)" Co&#=s od&l&s

INTRODUCTION

ar*o# #a#o(&*es ha!e remarDa*le ele(ro#i"

(hermal" a#d meha#ial proper(ies <hih a#

i#$l&e#e ma#) di$$ere#( *ra#hes o$ sie#e

a#d (eh#olo). The m&l(i<alled ar*o# #a#o

(&*es ,T=s- <ere $irs( prod&ed *) ima i#

1991 *) (he &se o$ ar dishare me(hod 1"

<hile (he si#le<alled ar*o# #a#o(&*es <ere

diso!ered i# 199'. These #a#oma(erials ha!e

$o&#d a <ide !arie() o$ applia(io#s s&h as

$il(ers" mem*ra#es" as adsor*e#(s" a(al)s(

s&ppor(s" miroele(ro#i de!ies" e(. 2.

Ge#erall)" ar*o# #a#o(&*es a# *e prod&ed

*) (he &se o$ (hree di$$ere#( me(hods <hih

i#l&de laser a*la(io#" ar dishare me(hod"

a#d hemial !apor deposi(io# ,>?- '7. The

las( me(hod ,>?-" amo# (hese me(hods" has

*ee# D#o<# as (he *es( me(hod $or (he laresale prod&(io# o$ T=s" si#e i( is simple"

os(e$$e(i!e" a#d hihl) e$$iie#( a#d #eeds

lo<er (empera(&re 81'. o<e!er" &#$or(&

#a(el)" si#e i# (he >? me(hod ar*o# #a#o

(&*es ro< i# a(al)s( (ips" me(al par(iles o&ld

8/11/2019 Jpst 2014 Vol. 4 No. 1



Science and Technology R. Ho($i" A. . Rashidi" a#d . ohse##ia

Journal of Petroleum Science and Technology 2014" 4,1-" 5560 h((p://ps(.ripi.ir


5' (

&s&all) *e o*ser!ed i# (he prod&ed T *odies.

oreo!er" some imp&ri(ies s&h as amorpho&s

ar*o# or o(her #a#os(r&(&red ar*o#s liDe

$&llere#es a#d ar*o# #a#o$i*ers are o*ser!ed.

# ma#) e#d&se applia(io#s" i( is desira*le (o&se hihp&ri() #a#o(&*es o#(ai#i# mi#imal

amo&#(s o$ resid&al a(al)s( me(al a#d s&ppor(

ma(erial a#d ex(ra#eo&s ar*o#. e#e (he

p&ri$ia(io# proess is a #eessar) a#d r&ial

s(ep i# order (o remo!e resid&al a(al)s(

par(iles a#d amorpho&s ar*o#s a#d o*(ai#

hihB&ali() desired #a#o(&*es. Al(ho&h some

s&h s(&dies ha!e pre!io&sl) *ee# arried o&(

1421" (o (he a&(hors= D#o<lede" i( has #o(

)e( *ee# impleme#(ed $or (he s)s(em &sed i#

(his <orD.

# (he prese#( <orD" m&l(i<alled ar*o# #a#o

(&*es <ere s)#(hesied *) dissoia(io# o$ me(h

a#e a#d #a(&ral as o!er a oo/; #a#o

a(al)s( i# a $l&idied *ed rea(or. The i#$l&e#e

o$ di$$ere#( om*i#a(io#s o$ p&ri$ia(io# me(hods

s&h as oxida(io# a#d aid (rea(me#(s o# (he

B&ali() o$ ar*o# #a#o(&*es <as i#!es(ia(ed (o

$i#d (he op(im&m me(hod $or (he p&ri$ia(io#.Rama# spe(rosop) <as &(ilied as (he meas&re

me#( (ool" si#e i( has pro!ed (o *e a #o#

des(r&(i!e a#d #o#dissipa(i!e hara(eria(io#

me(hod $or lo<er dime#sio#al ma(erials liDe

#a#oma(erials. Ree#(l)" i( has <idel) *ee# &sed

$or (he s(&d) o$ ar*o# #a#os(r&(&res s&h as

ar*o# #a#o(&*es. # addi(io#" (he appare#(

Co&#=s mod&l&s o$ T=s <as al&la(ed *)

(he &se o$ i#(e#si() ra(io ID/IG o*(ai#ed $rom

Rama# spe(ra da(a.

EXPERIMENTAL

# (he &rre#( <orD" a oo/; #a#oa(al)s(

<as sele(ed as (he a(al)s( o$ ar*o# #a#o(&*e

ro<(h" *ea&se ; s&ppor( o&ld &s&all) *e

elimi#a(ed easier (ha# o(her s&ppor(s s&h as

silia a#d al&mi#a 22" leadi# (o (he red&(io#

o$ p&ri$ia(io# os(s. This #a#oa(al)s( <as

prepared *) &si# a speial solel me(hod 2'.

The a(al)s(s <ere shaped i# spherial *eads (o

pre!e#( (heir erosio# i#side (he $l&idied *ed

rea(or. A$(er a(al)s( loadi# s(ae" (he) <ere

red&ed. A$(er red&(io#" (he (rea(me#( o$ (he

a(al)s( <as per$ormed *) (he &se o$ a mix(&reo$ h)droe# a#d #i(roe# $lo<" a#d (he# (he

me(ha#e or #a(&ral as $lo< <i(h a dil&(er <as

$ed (o (he rea(or. The rea(io# <as (aDe# plae

a#d (he prod&(s ame o&( o$ (he )lo#e

o#(i#&o&sl). The experime#(al se( &p $or

ar*o# #a#o(&*e ro<(h is sho<# i# Fi&re 1.

The rea(or <i(h a# i##er diame(er o$ 20 mm

a#d a heih( o$ 1"400 mm is made o$ B&ar(. For

dis(ri*&(i# (he as a#d holdi# (he #a#oa(al)s(

par(iles" a poro&s B&ar( dis has *ee# &sed.

The as e#(ers (he rea(or a$(er a prehea(i#

se(io#. The rea(or is plaed i# a proramma*le

!er(ial $&r#ae. Asprepared prod&(s <ere

a#al)ed &si# sa##i# ele(ro# mirosop)

,E- a#d ra) di$$ra(io# ,R?- (he res&l(s o$

<hih are sho<# i# Fi&res 2 a#d ' respe(i!el).

As i( is o*!io&s $rom (hese $i&res" some

imp&ri(ies are prese#( i# (he asprepared

sample. For i#s(a#e" i# (he R? pa((er# ,Fi&re

'-" (he di$$ra(io# peaDs a( 2θ I2526 are

a((ri*&(ed (o ar*o# #a#o(&*es 24" <hile

o(hers are a((ri*&(ed (o (he a(al)s( s&ppor( a#d

me(al resid&es. e#e i( is #eessar) (o p&ri$)

(he ar*o# #a#o(&*es.

)igure 1 Schematic of the e+perimental setup, -1.

fluidi/ed $ed reactor" -2. cyclone" and -. product

container

CH4

H2

The rea(io# &ses a h)droar*o#so&re ,me(ha#e- (o *e o#!er(ed(o h)droe# a#d ar*o##a#os(r&(&re emplo)i# a hih(empera(&re a#d a(al)s(.4 J 2 + Teside h)droe# prod&ed i# (he

o&(le(" i#p&( h)droe# is &sed as(he arrier as.

8/11/2019 Jpst 2014 Vol. 4 No. 1


Journal of PetroleumA Rioro&s ompariso# o$ e(hods $or &l(i<alled ar*o# K Science and Technology



( 5

)igure 2 S# photograph of the as3prepared multi3

&alled car$on nanotu$e

)igure 3ray analysis of the as3prepared multi3&alled car$on nanotu$e

Three di$$ere#( p&ri$ia(io# me(hods are applied

i# (his s(&d)" #amel) oxida(io#" h)drohlori

aid (rea(me#(" a#d #i(ri aid (rea(me#(. ore

o!er" *ased o# (he pre!io&s experie#e" (he

e$$e(s o$ (he om*i#a(io# o$ (hese me(hods

a#d (heir seB&e#es are dis&ssed. ;xida(io#

proess a# remo!e (he amorpho&s ar*o#s a#d

aid (rea(me#( a# elimi#a(e a(al)s( par(iles.


Ta*le 1 sho<s (he six samples &sed i# (his s(&d).

ample 1 is (he asprepared T <i(ho&( a#)

p&ri$ia(io#" <hile a( leas( o#e p&ri$ia(io#

me(hod is applied o# (he o(her samples. A$(er

per$ormi# di$$ere#( experime#(s" i( <as $o&#d

(ha( (he op(im&m o#di(io# $or oxida(io# pro

ed&re <as a (empera(&re o$ '00 L a#d (ime o$

'0 mi#&(esM $or l (rea(me#( (he op(im&m

o#di(io# <as 6 molar aid <ash a( 50 L $or 16

ho&rs <hile i( <as '.5 molar aid <ash a( 60 L

$or ' ho&rs $or ;' (rea(me#(.

Ta$le 1 Si+ different #6T samples &ith different

purification methods

Sample Step 1 Step 2 Step

1

2 ;xidied

' ;xidied l(rea(ed

4 ;xidied l(rea(ed ;'(rea(ed

5 l(rea(ed ;'(rea(ed ;xidied

6 ;xidied ;'(rea(ed l(rea(ed

The Rama# spe(ra are &sed $or &#ders(a#di#

(he B&ali() o$ ar*o# #a#o(&*es. ( sho&ld *e

#o(ed (ha( (he ? *a#d a( a*o&( 1'40 mN1

is

a((ri*&(ed (o s)mme(r)lo<eri# e$$e(s s&h as

de$e(s or de$orma(io# !i*ra(io#s o$ a hexao#al

ri# a#d (he prese#e o$ (he amorpho&s ar*o#"

<hile (he G *a#d a( a*o&( 1580 mN1

<a!e

le#(h is assi#ed (o a si#le r)s(alli#e $orm o$

raphi(e. The G= *a#d appears a( a*o&( 2690

mN1

a#d sho<s (he o!er(o#e o$ ?*a#d. The

ra(io o$ G *a#d i#(e#si() (o ? *a#d i#(e#si(),IG/ID- i#dia(es (he B&ali() o$ (he prod&(s. The

hiher (he ra(io is" (he hiher (he B&ali() o$ (he

prod&(s <o&ld *e. Fi&re 4 sho<s (he Rama#

spe(ra o$ six samples.

)igure 4 aman spectra of si+ #6T samples

The IG/ID ra(io is al&la(ed $or !ario&s samples

a#d (he res&l(s are sho<# i# Ta*le 2. As see# i#

(his (a*le" (he asprepared sample has a# IG/ID

8/11/2019 Jpst 2014 Vol. 4 No. 1






57 (

ra(io o$ 1.01. This ra(io i#reases $or samples 2"

'" a#d 4" <hile i( dereases $or samples 5 a#d 6.

The op(im&m sample is #&m*er 4" <i(h a# IG/ID

ra(io o$ 1.28" p&ri$ied *) oxida(io#" l (rea(

me#( a#d ;' (rea(me#( respe(i!el). Fi&re 5represe#(s (he R? pa((er# o$ (his sample"

<hih pro!es (he elimi#a(io# o$ a(al)s( s&ppor(

a#d par(iles.

)igure 5 3ray analysis of optimum multi3&alled

car$on nanotu$e

Ta$le 2 aman spectroscopy results of the #6T

samples

Sample 8 9 9: I D I G I D;I G

1 1''' 1582 2691 82.2' 8'.10 1.01

2 1'29 1564 269' 81.18 94.18 1.16

' 1'25 1577 2689 71.26 90.52 1.27

4 1'50 157' 2689 74.48 95.91 1.28

5 1'25 1595 2695 111.10 88.60 0.79

6 1'26 1588 2740 108.54 9'.75 0.86

( sho&ld *e me#(io#ed (ha( (he res&l(s are

o#sis(e#( <i(h (he $a( (ha( m&l(i<alled

ar*o# #a#o(&*es ha!e smaller !al&es o$ IG/ID i#ompariso# <i(h si#le<alled ar*o# #a#o

(&*es.

T=s are &s&all) prod&ed a( lo<er (emp

era(&res" a#d *ea&se o$ o#(ai#i# se!eral

la)ers" (he imp&ri(ies *e(<ee# la)ers are hardl)

elimi#a(edM ho<e!er" T=s are s)#(hesied a(

hiher (empera(&res a#d o#(ai# less imp&ri()

25.

Fi#all)" (he Co&#=s mod&li are al&la(ed *) (he

&se o$ a# empirial rela(io#" s&es(ed *)

E#omo(o e( al. 26:

1

4

.6

2.7 10 D

a

G

I E

I

−

= ×

,1-

<here" E a is Co&#=s mod&l&s i# 3a a#d ID/IG is

(he r)s(alli#i() $a(or o*(ai#ed $rom Rama#

spe(ra. The al&la(ed Co&#=s mod&li are

repor(ed i# Ta*le '. The res&l(s are i# aree

me#( <i(h li(era(&re 26. F&r(hermore" i( is

o*!io&s (ha( sample 4 has (he hihes( Co&#=s

mod&l&s.

Ta$le esult of <oung:s modulus of the #6T

samplesSample I D I G I D;I G E a

1 82.2' 8'.10 0.99 27458.'2

2 81.18 94.18 0.86 '4244.88

' 71.26 90.52 0.79 '9587.17

4 74.48 95.91 0.78 40459.85

5 111.10 88.60 1.25 18798.78

6 108.54 9'.75 1.16 21'56.74

CONCLUSIONS

&l(i<alled ar*o# #a#o(&*es <ere s)#(he

sied *) (he &se o$ a(al)(i hemial !apor

deposi(io# o!er a oo/; #a#oa(al)s( i# a

$l&idied *ed rea(or. The i#$l&e#es o$ di$$ere#(

om*i#a(io#s o$ p&ri$ia(io# me(hods a#d (heir

seB&e#es o# (he B&ali() o$ (he ar*o# #a#o

(&*es <ere e!al&a(ed a#d (he op(im&m

p&ri$ia(io# <as repor(ed. 3&ri$ia(io# me(hods

i#l&ded oxida(io#" l (rea(me#( a#d ;'

(rea(me#(. The sample <hih <as p&ri$ied *)oxida(io#" l (rea(me#(" a#d ;' (rea(me#(

respe(i!el) had (he lares( IG/ID !al&e o$ 1.28 as

<ell as (he lares( Co&#=s mod&l&s o$ 40459.85

3a.

ACKNOWLEDGMENT

This <orD <as s&ppor(ed *) a ra#( pro!ided *)

Researh #s(i(&(e o$ 3e(role&m #d&s(r) ,R3-.

8/11/2019 Jpst 2014 Vol. 4 No. 1


Journal of PetroleumA Rioro&s ompariso# o$ e(hods $or &l(i<alled ar*o# K Science and Technology



( 5=

NOMENCLATURE

T &l(i<alled ar*o# #a#o(&*es

T i#le<alled ar*o# #a#o(&*es

a.&. Ar*i(rar) &#i(

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odi$ied <i(h Aids a#d ;x)$l&ori#a(io#"P

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&s&mei A. ." ala<iD E. R." a#d Ra)

F. H." OA ompara(i!e (&d) o$ i#le

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Teh#iB&es si# Rama# pe(rosop)"P

S)ectrochim! cta Part " 2007" &*" 140

142.

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Ha$i H." osseme#( ?." a#d hahi#e R."

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ha#es ?&ri# 3&ri$ia(io# o$ i#le

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aQe#ie Q." ?&#e#s ;." a#d arris A. T."

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18 Hi& ." pe#er %. H." Qaiser A. ." a#d

Ar#old . ." Oele(i!e 3&ri$ia(io# o$

&l(i<alled ar*o# a#o(&*es *)

?iele(rophoresis <i(hi# a Hare Arra)"P

"urrent ))lied Phy'ic'" 200'" 6" 4274'1.

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al." O&l(i<alled ar*o# a#o(&*es

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20 iam*elli 3." a##i#o ?." ar#o ." a#d

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E$$e(i!e iro<a!e 3&ri$ia(io# a#d

F&#(io#alia(io# o$ &l(i<alled ar*o#

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'0 (

a#o(&*es"P Thin Solid ilm'" 2011" 5*+"

212121'1.

21

i#lo# H." Cihe ." Himi# ." a#d & ."

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&l(i<alled ar*o# a#o(&*es"P ))lied

Surface Science" 201" #&6" 159166.

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ai# R." mall . R." Co&# . A." >alleXs

." e( al." O)#(hesis a#d hara(eria(io#

o$ ;p(iall) A(i!e 3ol)a#ili#e ar*o#

a#o(&*e omposi(es"P /acromolecule',

200'" 3+" 7'24.

2' Rashidi A. ." AD*ar#ead . ."

Qhodadadi A. A." or(aa!i C." e( al."

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)#(hesied si# ;ra#i Addi(i!es (o oo a(al)s(s &ppor(ed o# a#oporo&s

;"P J! Nanotechnol!" 200" *$, '15605.

24 3aD T. %." a#eree ." e##) T. ." a#d

o# . ." O3&ri$ia(io# (ra(eies a#d

3&ri() >is&alia(io# Teh#iB&es $or i#le

<alled ar*o# a#o(&*es"P J! /ater!

"hem." 200'" *6" 141154.

25

;&)a# C." o# H. ." he# H." Hi& S. ."

e( al." ORama# (&d) o# i#le<alled

ar*o# a#o(&*es a#d &l(i<alled ar

*o# a#o(&*es <i(h ?i$$ere#( Haser

Exi(a(io# E#eries"P Phy'ica E!" 2007" 4."

2'862'8.

26 E#omo(o Q." Qi(aDa(a ." Cas&hara T."

;h(aDe ." e( al." Oeas&reme#( o$

Co&#=s od&l&s o$ ar*o# a#o(&*es *)

a#opro*e a#ip&la(io# i# a Tra#s

missio# Ele(ro# irosope"P ))l! Phy'!(ett ." 200'" $$" 15'115.

8/11/2019 Jpst 2014 Vol. 4 No. 1




Roohollah Parvizi


Tel: +98 912 816 1561

Fax:+98 6 !526 "565

Article history

Receive#: $pril 2%& 2%1!

Receive# i' revi(e# )orm: *ovemer 2"& 2%1!

$ccep,e#: -ecemer 16& 2%1!

$vailale o'li'e: arch 1%& 2%1"

Journal of Petroleum Science and Technology 2014 , "/10& 6169 h,,p:3p(,.ripi.ir

4 2%1" Re(earch '(,i,,e o) Pe,rolem '#(,ry /RP0

61

AN EXPERIMENTAL INVESTIGATION OF GRAVITY DRAINAGE

DURING IMMISCIBLE GAS INJECTION IN CARBONATE ROCKS

UNDER RESERVOIR CONDITIONS

oohollah Par!i"i1* and #$rahim %hasemi &e'ad

2

1 (lamic $za# 7'iver(i,y e(hm ra'ch& Tehra'& ra'

2 *a,io'al ra'ia' o,h ;il <ompa'y /*;<0& $hvaz& ra'

ABSTRACT

=ravi,y #rai'a>e i( o'e o) ,he impor,a', recovery mecha'i(m( i' )rac,re# caro'a,e a'#

co've',io'al re(ervoir(. , occr( #e ,o #e'(i,y #i))ere'ce e,?ee' ,he >a( i' )rac,re a'# ,he oil

i' ma,rix a( ?ell a( i' co've',io'al ,il,e# re(ervoir(. ;il pha(e ?ill )orm )ilm( ?hich are pro#ce#'#er >ravi,y )orce( /)ilm )lo?0. a'y >a( i'3ec,io' experime',( have ee' #o'e o' laora,ory

(cale( ?i,h #ea# oil& ,& herei'& ?e ?ol# lie ,o recomi'e oil '#er re(ervoir co'#i,io'(. ' ,hi(

paper& ,he >ravi,y #rai'a>e proce(( i( co'(i#ere# #ri'> immi(cile >a( i'3ec,io' i' caro'a,e core

(a,ra,e# ?i,h recomi'e# oil a, re(ervoir ,empera,re a'# pre((re. Recomi'e# oil ?a(

prepare# )rom #ea# oil a'# a (olve', /me,ha'e a'# propa'e0 mixe# i' recomi'a,io' appara,(. '

,he(e experime',(& 'i,ro>e' >a( i( i'3ec,e# i' a (i'>le ma,rix loc a, #i))ere', ra,e( a'# #irec,io'(.

i'ce ,he recovery o) oil #epe'#( o' ,he >a( i'3ec,io' )lo? ra,e& ,he recovery o) oil i( maximize# a,

a (peci)ic )lo? ra,e. The re(l,( (ho? ,ha, >a( i'3ec,io' a, >ravi,y #rai'a>e ra,e >ive( ,he maximm

recovery& a'# l,ima,e recovery #ecrea(e( a, mch hi>her i'3ec,io' ra,e(. <ompari'> ,he >a(

i'3ec,io' re(l,( i' horizo',al a'# ver,ical #irec,io'( (ho?( ,ha, ,he recovery i( hi>her i' ,he ver,ical

#irec,io' ,ha' ,he horizo',al #irec,io'.

(ey)ords: mmi(cile =a( '3ec,io'& =ravi,y -rai'a>e& Recovery Fac,or

INTRODUCTION

E'ha'ce# oil recovery /E;R0 i( #e)i'e# a( ,he

pro#c,io' o) cr#e oil ,hro>h proce((e( ,o

i'crea(e ,he primary re(ervoir #rive. The(e

proce((e( may i'cl#e pre((re mai',e'a'ce&

,he i'3ec,io' o) #i(placi'> )li#(& or o,her

me,ho#( (ch a( ,hermal ,ech'iAe(. There)ore&

y #e)i'i,io'& E;R ,ech'iAe( i'cl#e all ,he

me,ho#( (e# ,o i'crea(e ,he cmla,ive pro

#ce# oil /oil recovery0 a( mch a( po((ile B1C.

=ravi,y #rai'a>e i( ,he mai' mecha'i(m o)

pro#c,io' i' )rac,re# re(ervoir(. -e'(i,y #i)

)ere'ce e,?ee' ,he oil i' ma,rix a'# ,he >a( i'

)rac,re ca(e( oil pro#c,io' ',il ,he >ravi,y

)orce( a'# capillary )orce( reach a' eAilirim

i' ,he poro( me#ia B2C.

' a##i,io' ,o )rac,re# re(ervoir(& >ravi,y

#rai'a>e ca' occr i' ,il,e# co've',io'al re(er

voir(. mmi(cile >a( i'3ec,io' i( employe#

herei'D 'i,ro>e' i( immi(cile ?i,h oil a, pre(

(re( elo? 5%%% p(i B2C a'# ,h( i, ?a( (elec,e#

8/11/2019 Jpst 2014 Vol. 4 No. 1



Science and Technology R. Parvizi a'# E. =ha(emi *e3a#

Journal of Petroleum Science and Technology 2014& "/10& 6169 h,,p:3p(,.ripi.ir


62

a( a' immi(cile >a( ,o e i'3ec,e# ,o ,he core(.

' )ormer (,#ie(& >a( ?a( i'3ec,e# ,o >la((

micromo#el( i' or#er ,o (ee #i(placeme',

mecha'i(m& a'# experime',( ?ere al(o carrie#

o, o' core (cale( '#er re(ervoir co'#i,io'(.The crre', (,#y )ollo?( )ormer ?or( ?i,h a

)or?ar# (,ep a'# he'ce ,he experime',( are

per)orme# y (i'> recomi'e# oil '#er

re(ervoir co'#i,io'( /pre((re a'# ,empera,re0

i' ,he pre(e'ce o) co''a,e ?a,er (a,ra,io'.

' or#er ,o (ee >ravi,y #rai'a>e '#er re(ervoir

co'#i,io'(& i, i( impor,a', ,o pay a,,e',io' ,o

veloci,y #i(placeme', '#er re(ervoir co'#i

,io'(. eloci,y #i(placeme', i' re(ervoir i( very

lo? /1 ),#ay0. For ,he compari(o' o) veloci,y

#i(placeme', o' re(ervoir (cale a'# core (cale&

#ime'(io'le(( parame,er( lie capillary 'mer

are (e# B2C.

c

V N

µ

σ

×= /10

?here& V i( veloci,y a'# σ i( ,he (r)ace ,e'(io'

e,?ee' ,he i'3ec,e# )li# a'# re(ervoir )li#D μ repre(e',( vi(co(i,y.

<apillary 'mer )or )li# )lo? '#er re(ervoir

co'#i,io'(& Nc& i( le(( ,ha' 1%

D ,h( )or ,he

(imla,io' o) )li# )lo? '#er ac,al re(ervoir

co'#i,io'( ?i,h experime',al core #a,a& i'3ec,

,io' )lo? ra,e (hol# e (elec,e# i' (ch a ?ay

,ha, capillary 'mer varie( i' ,he proper ra'>e.

$ cri,ical >a( i'3ec,io' )lo? ra,e i( #e)i'e# i'

(,#ie( o) ra,e (e'(i,ivi,y a'aly(i(. $, cri,ical

i'3ec,io' )lo? ra,e >ravi,y& capillary a'# vi(co(

)orce( i',erac, i' (ch a ?ay ?hich re(l,( i' ,he

maximm oil recovery. $, i'3ec,io' ra,e( lo?er

,ha' ,he cri,ical ra,e& capillary )orce( #omi'a,e

vi(co( )orce( a'#& #e ,o capillary )orce(& (ome

o) ,he oil i( ,rappe# i' ,he core. For i'3ec,io'

ra,e( >rea,er ,ha' ,he cri,ical ra,e& )i'al recovery

#ecrea(e( eca(e o) )i'>eri'> a'# a #ecrea(e i'

pi(,o'lie #i(placeme', B!C.

Ter?illi>er e, al. repor,e# ,he re(l, o) (al,

?a,erair #i(placeme', i' a 1! ), pace# (a'#

colm' ?i,h hi>h permeaili,y a, a co'(,a',

pre((re o) 5% p(i a, #i))ere', )lo? ra,e( B"C.

ohamma#i e, al. per)orme# a' i've(,i>a,io'

o' ,he immi(cile recycle >a( i'3ec,io' a( a'

E;R (ce'ario )or improvi'> recovery e))icie'cy

i' o'e o) ,he (o,h?e(, ra'ia' oil re(ervoir(.

They co'cl#e# ,ha, ,he comple,io' o) i'3ec,io'

?ell( i' )rac,re a'# pro#c,io' ?ell( i' ma,rix

ha# e,,er oil)iel# e))icie'cy i' compari(o' ,o

o,her ca(e( B5C.

a>hi>hi a'# Gor,(o( (,#ie# ,he oil #i(place

me', y >a(. Their experime',al re(l,( (ho?e#,ha, a( i'3ec,io' )lo? ra,e #ecrea(e#& capillary

)orce( ,o vi(co( )orce( ra,io i'crea(e# a'#

#i(placeme', ?a( more (,ale& ?hich ?a(

co'(i#ere# a( ,he ca(e o) ,rappi'> oil a, hi>h

i'3ec,io' ra,e(. a>hi>hi e, al. poi',e# ,o ,he

exi(,e'ce o) a cri,ical i'3ec,io' )lo? ra,e a( ,he

mi'imm i'3ec,io' ra,e reAire# )or havi'> a

a(e recovery B6C.

oro(h a'# ai#i carrie# o, experime',( o' acaro'a,e core ?i,h a le'>,h o) 15%.9 cm a'# a

poro(i,y o) 16.5H ,o e(,ima,e ,he #y'amic

ehavior o) immi(cile #i(placeme', a'# mi(ci

le >a( a'# ,o (ho? ,he recovery po,e',ial o) a

re(ervoir ?i,h a permeaili,y o) 1 m#. ;il

recovery a, i'3ec,io' ra,e( o) 1 a'# 1% cchr ?a(

"H a'# 62H re(pec,ively. They al(o i've(,i

>a,e# ,he e))ec, o) >a( oil ra,io /=;R0 a'# >a(

compo(i,io' #ri'> >a( i'3ec,io' BC.

The(e i'3ec,io' ra,e( are (everal ,ime( >rea,er

,ha' >ravi,y (,ale )lo? ra,e )or ,hi( lo? perme

aili,y core. Thi( mea'( ,ha, >a( i'3ec,io' a, )lo?

ra,e( >rea,er ,ha' >ravi,y (,ale )lo? ra,e ca'

pro#ce( more ,ha' 6%H o) ori>i'al oil i' place.

' )rac,re# re(ervoir( ?i,h lo? ,hre(hol#& oil

recovery ca' reach ,he maximm vale ?hich i(

a( lar>e a( recovery '#er >ravi,y #rai'a>e

mecha'i(m B6C.

8/11/2019 Jpst 2014 Vol. 4 No. 1


Journal of Petroleum$' Experime',al 've(,i>a,io' o) =ravi,y -rai'a>e I Science and Technology



6+

EXPERIMENTALS

Recombined Oil Preparation

Recomi'e# oil ?a( prepare# )rom (olve', a'#

#ea# oil y (i'> recomi'a,io' appara,(

/Tale 10. olve', ?a( prepare# y (olve',

appara,(& a'# compo(i,io' o) (olve', ?a( 19.2

>r me,ha'e a'# 1.6 >r propa'e& ?hich ?a(

i'3ec,e# ,o ,he cyli'#er o) (olve', appara,( /25

mol.H propa'e a'# 5 mol.H me,ha'e0.

Ta$le 1, ecom$ined oil parameters

-u$$le point

pressure .psi/

at 60 C

ρ

.grcm+/

μ

.cp/% Bo

Solution

gas

compounds

19%%

%.65

1.!8

58.8

1.15

H25 <"

H5 <!8

$),er ope'i'> ,he >a(oil recomi'a,io' cell a'#

clea'i'> i,& 5%% cc o) $h?az #ea# oil ?a( pore#

i',o i, a'# ,he cell ?a( clo(e#. The'& ,he

prepare# (olve', ?a( mixe# ?i,h #ea# oil a'#

,he cell ,empera,re a'# pre((re ?ere (lo?ly

rai(e# aove i,( le poi', pre((re ',il a

(i'>le pha(e )li# ?a( o,ai'e#.

Core PreparationThe(e experime',( ?ere co'#c,e# o' a

caro'a,e core. $ cyli'#rical (ample core ?a(

prepare# y core (ampler appara,(. The

a(ol,e permeaili,y o) core ?a( mea(re# a,

#i))ere', ?a,er i'3ec,io' )lo? ra,e( y (i'> o)

-arcy )ormla /Fi>re 10:

3igure 1, A$solute core permea$ility .)ater/

w

w

k A P

q L µ

∆

= − /20

?here& L& A& a'# k w are ,he le'>,h o) core& ,he

cro(( (ec,io' area o) core& a'# ,he permeaili,y

o) ?a,er re(pec,ively. q& P& a'# !w repre(e',

)lo? ra,e& pre((re #i))ere'ce& a'# ,he vi(co(i,y

o) ?a,er re(pec,ively.

For mea(ri'> ,he oil )orma,io' volme )ac,or

/"#0& ,he volme o) ,he oil '#er re(ervoir a'#

a,mo(pheric co'#i,io'( i( reAire#. $' approxi

ma,e vale i( 1.15 lT a, 6% J< /Fi>re 20.

The charac,eri(,ic( o) ,he core are me',io'e# i'

Tale 2.

3igure 2, il formation !olume factor .Bo/

Ta$le 2, Core parameters

Core TypeK

.md/

L .cm/

A .cm2/ Connate )ater

saturation ./

Kime(,o'e %.1 2 1!.5 11.9"6 %.26

eve' experime',al r'( a, pre((re( o) !5%%&

!%%%& 25%%& 2%%%& 18%%& 15%%& a'# 125% p(i

?ere co'#c,e#. The volme o) i'3ec,e# >a( i(

plo,,e# ver(( pre((re /Fi>re !0. The le

poi', i( co'(i#ere# a( ,he poi', ?here ,he (lope

i( cha'>e#.

Gas Injection Experiments

The(e experime',( ?ere #o'e ?i,h hi>h

pre((re a'# ,empera,re <;REFK;;- appa

ra,( /maximm pre((re: 1%%%% p(i a'# maxi

mm ,empera,re: 2%% J<0. <ore ?a( co'

'ec,e# ,o a' i'3ec,i'> pmp )rom o'e (i#e

/i'p, li'e0 a'#& )rom ,he o,her (i#e& i, ?a(

co''ec,e# ,o ac pre((re appara,( i' ?hich

)li# exi,( )rom ,he core y a pro#c,io' li'e.

1.5%

1.%

1.9%

2.1%

2.!%

2.5%

% 5% 1%% 15% 2%%

P e r m e a $ i l i t y . m

5 /

3lo) ate .cchr/

L?

1

1.%5

1.1

1.15

1.2

1.25

1.!

1% 2% !% "% 5% 6%

B o

Time .min/

8/11/2019 Jpst 2014 Vol. 4 No. 1






64

3igure +, -u$$le point pressure .psi/

Core Preparation Process

$),er c,,i'> a'# prepari'> ,he core ?i,h aproper #iame,er& i, ?a( clea'e# a'# #rie#. The

core ?a( ?a(he# i' core ?a(hi'>machi'e a'#

#rie# i' ove' )or each experime',. Ma(hi'>

proce(( ?a( #o'e i' ?a(hi'> machi'e (i'>

,ole'e a'# <;2 >a( )or 8 ,o 1% hor(D ,he'& ,he

core ?a( place# )or 1% ,o 12 hor( i' ove' )or

comple,e #ryi'>. e)ore layi'> ,he core i' ,he

core hol#er& ,he core ?a( (eale# i' a pla(,ic

cover& ?hich hea,e# ,o (,ic ,o core& a'# ,he

core ?a( ,he' co''ec,e# ,o ,he core hol#er y

me,al )a(,e'er(.

Connate Water and Recombined Oil

' a##i,io' ,o pre((re a'# ,empera,re&

co''a,e ?a,er (a,ra,io' (hol# exi(, i' ,he

coreD ,h( ,he core ?a( (a,ra,e# ?i,h ?a,er ,o

crea,e co''a,e ?a,er (a,ra,io' i' i,. oreover&

overr#e' pre((re (hol# e applie# o' ,he

coreD ,hi( overr#e' pre((re ?a( (pplie# y

a pmp ?hich pmpe# ?a,er i',o ,he (hell

aro'# ,he core. ' ,he(e experime',(& over

r#e' pre((re ?a( al?ay( 2%% p(i >rea,er

,ha' ,he core pre((re. For ,he e,,er (a,ra,io'

o) core& ,he core ?a( vacme# y a (c,io'

pmp )or 5 hor( a'# ?a,er ?a( i'3ec,e# a, a

ra,e o) 2 cchr )rom ,he o,,om o) ,he core. "

pore volme( o) ?a,er ?ere i'3ec,e# ,o ,he

core. ea,i'> (y(,em ep, ,he ,empera,re o)

oil& >a( cyli'#er(& ?hich ?ere place# i' ,he ove'&

a'# ,he core hol#er (ec,io' a, 6% J<. The core

,empera,re ?a( i'crea(e# ,o 6% J< y ,he

(e'(or a'# hea,er eleme',( place# i' ,he core

hol#er. $),er (ome mi',e( ,he ,empera,re

(,ailize#.

$),er?ar#(& ,he core ?a( (a,ra,e# ?i,h

recomi'e# oil. i'ce ,he pre((re o) ,he oil

cyli'#er( (hol# e ep, a, a pre((re hi>her

,ha' ,he le poi', /19%% p(i& Fi>re !0 o)

recomi'e# oil (o ,ha, ,he >a( remai'( (olle

i' oil& ,he ac pre((re re>la,or /PR0 ?a( (e,

a, 2"%% p(i. The ac pre((re re>la,or

co',rolle# ,he o,le, pre((re o) core. ;il ?a(

'o, pro#ce# 'le(( i,( pre((re ?a( hi>her

,ha' ,ha, o) ,he ac pre((re re>la,or. The

pre((re o) core a'# overr#e' pre((re ?a(

(iml,a'eo(ly i'crea(e# (,ep y (,ep ,o 2"%%

p(i a'# 26%% p(i re(pec,ively. $( me',io'e#

aove& ,he overr#e' pre((re ?a( hi>her ,ha'

,he core pre((re y 2%% p(i i' or#er ,o ,i>h,ly

eep ,he core (leeve a'# preve', (leeve

rp,ri'>. $),er ,he pro#c,io' o) ?a,er )rom

PR a'# ,he (,ailiza,io' o) ?a,er i'3ec,io' a,

,he pre((re o) 2"%% p(i& ,he recomi'e# oil ?a(i'3ec,e# ,o core. eca(e oil #e'(i,y ?a( lo?er

,ha' ?a,er #e'(i,y& ,he recomi'e# oil ?a(

i'3ec,e# )rom ,he ,op o) ,he core y ro,a,i'> ,he

core hol#er ver,ically. Recomi'e# oil ?a(

i'3ec,e# ,o core a, a 2 cchr )lo? ra,e& a'# "

pore volme( o) recomi'e# oil ?ere i'3ec,e# ,o

,he core ,o a((re oil (a,ra,io'. <o''a,e ?a,er

(a,ra,io' o) oil ?a( calcla,e# y 'o?i'> ,he

pore volme o) ,he core a'# ,he ?a,er pro

#ce# )rom ,he core. ' mo(, o) ,he ca(e(& i, ?a(

#e,ermi'e# ,ha, immoile co''a,e ?a,er (a,

ra,io' ha# a (mall e))ec, o' ,he rela,ive permea

ili,y o) oil?a,er a'# oil recovery.

Gas Injection

=a( i'3ec,io' ?a( per)orme# y (i'> 'i,ro>e'&

,he (peci)ica,io'( o) ?hich are >ive' i' Tale !.

i'ce ,he (e# core ?a( caro'a,e roc ?i,h

very lo? permeaili,y& ,heore,ically o,ai'e#

y N 2%.6 $ "685."

y N 6."62 $ 159."2

%

1%%%

2%%%

!%%%

"%%%

15% 25% !5% "5%

P

. p s i /

olume .cc/

8/11/2019 Jpst 2014 Vol. 4 No. 1





67

cri,ical )lo? ra,e ?a( very lo?. i'ce >ravi,a

,io'al (,ale )lo? ra,e )or ,he (e# core i' ,he

ver,ical po(i,io' ?a( very lo?& >a( i'3ec,i'> ?a(

(,ar,e# a, a )lo? ra,e o) 1 cchr. , ?a( o(erve#

,ha, i'3ec,io' a, lo? )lo? ra,e( i'crea(e# oil

recovery& , a )r,her re#c,io' o) >a( i'3ec,io'

)lo? ra,e #i# 'o, lea# ,o hi>her vale( o) oil

recovery. There)ore& i' prac,ice& ,here i( 'o

'ee# ,o i'3ec, >a( a, very lo? )lo? ra,e( ,o have

hi>h recovery /Fi>re "0.

Ta$le +, 8n'ected gas parameters

%as

ρ .grcm+/ μ .cp/

*2 %.%%11" %.%15

3igure 4, Critical gas in'ection flo) rate

' or#er ,o )i'# ,he cri,ical >a( i'3ec,io' )lo?

ra,e& a, ?hich ,he maximm oil recovery occr(&

,e(,( ?ere co'#c,e# a, #i))ere', )lo? ra,e(. To

o(erve >ravi,y #rai'a>e i' ,he ver,ical po(i,io'&

oil recoverie( i' #i))ere', #irec,io'( ?ere

compare#. The core ro,a,io' (y(,em cha'>e#

,he #irec,io' o) >a( i'3ec,io'. ;il recoverie( a,

#i))ere', >a( i'3ec,io' )lo? ra,e( i' ,he ver,ical

a'# horizo',al #irec,io'( ?ere al(o compare#.i'ce ,he aim o) ,he(e experime',( ?a( ,o (ee

,he ver,ical >ravi,y #rai'a>e proce((& ,he hori

zo',al ,e(,( ?ere al(o co'#c,e# ,o e com

pare# ?i,h ,he ver,ical o'e(. =a( i'3ec,io' )lo?

ra,e( o) 1& 2& 5& a'# 1% cchr ?ere (elec,e# )or

,he ver,ical mo#e a'# )lo? ra,e( o) 5 a'# 1%

cchr ?ere (elec,e# )or ,he horizo',al mo#e.

Fi>re 5 (ho?( recovery ver(( ,ime a, a )lo?

ra,e o) 5 cchr i' ,he ver,ical #irec,io'. For ,he

compari(o' o) #i))ere', )lo? ra,e( i' ,he ver,ical

#irec,io'& ,he varia,io' o) oil recovery ver((

,ime i( (ho?' i' Fi>re 6. The recoverie( are

pre(e',e# ver(( pore volme i'3ec,e# a'#

capillary 'mer( are al(o calcla,e# /Fi>re 0.

Fr,hermore& ,he horizo',al a'# ver,ical recov

erie( a, ,he (ame i'3ec,io' )lo? ra,e are com

pare#. Fi>re( 8 a'# 9 compare oil recoverie(

ver(( pore volme i'3ec,e# i' ,he horizo',al

a'# ver,ical #irec,io'( a, >a( i'3ec,io' )lo? ra,e(

o) 5 a'# 1% cchr re(pec,ively.

3igure 7, Critical reco!ery !ersus time in the !ertical

direction at a flo) rate of 7 cchr

3igure 6, eco!ery !ersus time at different flo)

rates in the !ertical position

3igure 9, eco!ery !ersus in'ected pore !olume at

different capillary num$ers in the !ertical position

6"."

61.61

5%.2 "!.!6

!%

"%

5%

6%

%

% ! 6 9 12

: l t i m a t e e c o ! e r y . 4 /

3lo) ate .cchr/

%

1%

2%

!%

"%

5%

6%

% 6%%% 12%%% 18%%% 2"%%% !%%%%

e c o ! e

r y . 4 /

Time .s/

%

1%

2%

!%

"%

5%

6%

% 5%%%% 1%%%%% 15%%%%

e c o ! e r y . 4

/

Time .s/

; < 1 cchr

; < 2 cchr

; < 7 cchr

; < 10 cchr

%

1%

2%

!%

"%

5%6%

%.%% %.!% %.6% %.9% 1.2% 1.5%

e c o ! e r y . 4 /

Pore olume 8n'ection

&c < 6=2+ # >?

&c < 1=27 # >9

&c < +=12 # >9

&c < 6=2+ # >9

8/11/2019 Jpst 2014 Vol. 4 No. 1






66

3igure ?, Comparison of reco!ery in the !ertical and

the hori"ontal positions at a gas flo) rate of 7 cchr

3igure @, Comparison of reco!ery in the !ertical and

the hori"ontal positions at a gas flo) rate of 10

cchr

For >a( i'3ec,io' a, each )lo? ra,e& ,he core

hol#er ?a( ro,a,e# i' ,he proper #irec,io' a'#

,he pre((re o) 'i,ro>e' >a( cyli'#er ?a(

reache# ,he (,ea#y (,a,e pre((re o) ,he core.

The i'3ec,io' ra,e ?a( (e, ,o each )lo? ra,e& a'#&

a),er clo(i'> recomi'e# oil i'3ec,io' li'e&

'i,ro>e' >a( ?a( i'3ec,e# ,o ,he core. ;il ?a(

pro#ce# a'# mea(re# i' >la((e(. =a( '3ec,io'

?a( co',i'e# ',il 'o more oil ?a( pro#ce#&D

(ally a),er 1.5 pore volme( o) >a( i'3ec,io'

,here ?a( 'o oil pro#c,io'. $),er oil pro#c,io'

)i'i(he#& >a( i'3ec,io' ?a( (,oppe#D ,he >a(

i'p, valve ?a( ,he' clo(e#D 'ex,& pre((re

(y(,em ?a( (lo?ly #roppe# ,o a,mo(pheric

pre((re& a'#& )i'ally& ,he core hol#er ?a(

ope'e#. Fr,her ,e(,( ?ere carrie# o, (i'> ,he

(ame me,ho#.

The re(l,( a'# #ia>ram( o) recovere# oil )rom

,he core a'# recoverie( i' ,he horizo',al a'#

ver,ical po(i,io' ?ere >raphically compare#. The

plo, o) l,ima,e oil recoverie( ?i,h re(pec, ,o

>a( i'3ec,io' )lo? ra,e( (ho?( ,ha,& a, a (peci)ic

>a( i'3ec,io' )lo? ra,e& l,ima,e oil recovery i(

maximize#. 7l,ima,e oil recoverie( ?i,h re(pec,,o >a( i'3ec,io' )lo? ra,e( are (ho?' ' Fi>re ".

The (,#ie( (ho? ,ha, i'3ec,i'> a, a (,ale

>ravi,y #rai'a>e )lo? ra,e re(l,( i' ,he maxi

mm recovery. i'ce i'3ec,io' a, >ravi,y #rai'

a>e )lo? ra,e ,ae( a lo, o) ,ime& i'3ec,io' a,

(ch a )lo? ra,e i( 'o, prac,ical. ;) cor(e& i) >a(

i( 'o, i'3ec,e# a, (ch a )lo? ra,e& o'e may 'o,

lo(e a lo, o) recovery. , mea'( ,ha, i) ,he

i'3ec,io' ra,e i( (,ale >ravi,y #rai'a>e& ,he

maximm oil recovery #oe( 'o, i'crea(e (o

mch. $( ca' e (ee' )or ,he i'3ec,io' )lo? ra,e(

o) 1 a'# 2 cchr /Fi>re( 6 a'# 0& oil recovery

#oe( 'o, i'crea(e( very mch eve' ?he' ,he

)lo? ra,e i( #ecrea(e# y hal). The ,re'# o)

i'crea(i'> oil recovery y #ecrea(i'> ,he i'3ec,

,io' )lo? ra,e i( (ho?' i' char,(. , i( expec,e#

,ha, a, (,ale >ravi,y #rai'a>e i'3ec,io' )lo?

ra,e& ,he maximm oil recovery i( o,ai'e#.


mmi(cile #i(placeme', a, #i))ere', )lo? ra,e(

(ho?( ,ha, ,he recovery i( >rea,er i' ,he ver,ical

po(i,io' ,ha' ,he horizo',al po(i,io'& )rom

?hich i, i( expec,e# ,ha, )ilm )lo? play( a role i'

,he ver,ical po(i,io' a),er ,he #i(placeme', o)

,he ma((. i>her oil recovery o,ai'e# y

immi(cile #i(placeme', i' ,he ver,ical po(i,io'

ca' e #e ,o ,he e))ec,ive )ilm )lo? phe'ome

'o'.

$, hi>h pre((re(& recovere# oil i'crea(e( #e ,o

a' i'crea(e i' )orma,io' volme )ac,or /FF0

a'# a #ecrea(e i' re(i#al oil (a,ra,io' )or

lo?er i',er)acial ,e'(io' /FT0. , i( expec,e# ,ha,

i) ,he core i( allo?e# ,o e #rai'e# i' (pecial

circm(,a'ce(& ,he mecha'i(m o) )ilm )lo? co'

,i'e( a),er (,oppi'> ,he i'3ec,io' o) ,he >a(. ,

(hol# e 'o,e# ,ha, ,hi( proce(( occr( i) ,he

>ravi,y )orce( overcome capillary )orce(.

%

1%

2%

!%

"%

5%

%.%% %.!% %.6% %.9% 1.2% 1.5%

e c o

! e r y . 4 /


Forizo',al

er,ical

%

1%

2%

!%

"%

5%

%.%% %.!% %.6% %.9% 1.2% 1.5%

e c o ! e r y . 4 /


Forizo',al

er,ical

8/11/2019 Jpst 2014 Vol. 4 No. 1





69

There)ore& ,he recovery mea(re# a),er ,he

i'3ec,io' o) 1.5 pore volme( (hol# 'o, e

,ho>h, a( ,he l,ima,e recycli'>. Thi( i( o'e

rea(o' )or recovery i'crea(i'> a, lo?er i'3ec,io'

)lo? ra,e(. ;il recovery >raph( (ho? ,ha, hi>her

recovery i( o,ai'e# a, lo?er i'3ec,io' )lo?

ra,e(. $l,ho>h i'3ec,io' )lo? ra,e i( co'(i#er

aly lo?er ,ha' (,ale >ravi,y #rai'a>e )lo?

ra,e& recovery i( hi>her ,ha' 6%H. The ver,ical

(,ale >ravi,y #rai'a>e )lo? ra,e i( o,ai'e# y:

g K q

ρ

µ

∆ × ×= /!0

q& %&& a'# g (,a'# )or )lo? ra,e& #e'(i,y

#i))ere'ce e,?ee' oil a'# >a(& a'# >ravi,yaccelera,io' re(pec,ively. ' a'# ! expre(( per

meaili,y a'# vi(co(i,y corre(po'#i'>ly. $),er

co'ver,i'> #a,a ,o c.>.(. (y(,em& ver,ical (,ale

>ravi,y #rai'a>e )lo? veloci,y /u0 i( eAal ,o:

0.002 (0.65 0.00114) 980 3600

1.38 1013250

0.00327

u

cm

hr

× − × ×=

×

=

/!0

'3ec,io'( a, )lo? ra,e( o) 1 a'# 1% cchr& ?hich

are corre(po'#i'>ly propor,io'al ,o %.%8" a'#

%.8! cmhr& are 25 a'# 255 ,ime( hi>her ,ha'

(,ale >ravi,y #rai'a>e )lo? ra,e re(pec,ively.

' a##i,io' ,o ,he e))ec, o) i'3ec,io' ra,e o'

recovery& ?e,,aili,y a))ec,( ,he re(i#al oil

(a,ra,io'. , i( expec,e# ,ha, pre)eraly ,he oil

?e, core( have more remai'i'> oil ,ha' ,he

?a,er?e, core(. $l,ho>h hi>h oil recovery ?i,h

ver,ical >ravi,y #rai'a>e ca' e o,ai'e#& lo?

recovery ca' e #e ,o ,he )ollo?i'> rea(o'(:

1

'())icie', ,ime )or ,he )ilm )lo?D

2 i>h i'3ec,io' )lo? ra,e(& ?hich #o 'o, allo?

e,,er oil #i(placeme', y >a(. , ca' e #e

,o ,he >a( )i'>eri'> i' lo? permeaili,y

core(& a'# ca' ca(e ypa((i'> oil.

For ,he prac,ical applica,io' o) ,he(e experi

me',(& i, ca' e co'cl#e# ,ha, >a( i'3ec,io' ha(

>oo# recovery i' ,he re(ervoir( ?i,h lo?

permeaili,y a'# hi>h i'i,ial pre((re. Thre(hol#

hei>h, i( rela,ively (mall a, hi>h pre((re #e ,o

(mall i',er)acial ,e'(io'D )r,hermore& ,hi(

me,ho# i( more applicale ,o )rac,re#

re(ervoir( #e ,o (mall ,hre(hol# hei>h, i'

)rac,re(. For example& a 1%)ee, loc ha( ee'

mea(re# '#er a,mo(pheric co'#i,io'(D

,hre(hol# hei>h, i( 1 )oo, a'# i',er)acial ,e'(io'

i( !% m*mD a, ,he re(ervoir pre((re& i',er)acial

,e'(io' i( 2 m*m a'# ,hre(hol# hei>h, i( %.%6

)oo,. i'ce i' ,he )rac,re# re(ervoir(&

#i(placeme', i' ma,rix loc( occr( '#er

(,ale >ravi,y #rai'a>e& ,he maximm recovery

(hol# reach >ravi,y #rai'a>e recovery B2C. , i(

)oreca(,e# ,ha, >ravi,y #rai'a>e proce(( i( acomi'a,io' o) (i'>le pha(e )lo?& primary

#rai'a>e& a'# mai'ly a )ilm )lo? a),er #rai'a>e.

=ravi,y #rai'a>e ha( a hi>her rela,ive (pee# i'

)rac,re# re(ervoir( compare# ,o ,he (i'>le

poro(i,y re(ervoir(.

=a( i'3ec,io' ,o )rac,re# re(ervoir( o'ly pro

#ce( a )e? perce', o) oil i' ,he ma,rix loc.

-e ,o lo? permeaili,y o) re(ervoir roc& (ome

>a( e',er( ,he re(ervoir roc a'# ,he remai'e#

>a( ypa((e( loc( ?i,h lo? permeaili,y a'#

e',er( )rac,re( /i' (i'>le pha(e re(ervoir(& ,he

i'3ec,e# )li# pa((e( ,hro>h i',erco''ec,e#

pore(0. There)ore& >ravi,y #rai'a>e i( e))ec,ive i'

,he ex,rac,io' o) ,he remai'e# oil )rom ma,rix

loc(. $##i,io'ally& ,he ,hre(hol# hei>h, a'#

capillary charac,eri(,ic( o) re(ervoir roc /capil

lary pre((re0 are )ac,or( ?hich a))ec, >ravi,y

#rai'a>e. ' or#er ,o o,ai' capillary 'mer&

,he i',er)acial ,e'(io' o) ,he i'3ec,e# )li#/'i,ro>e'0 a'# oil i( reAire#. erei'& a )air

approxima,io' o) i',er)acial ,e'(io' o,ai'e# y

M*PR; (imla,or i( ao, 5.15 -y'ecm. $(

ca' e (ee'& capillary 'mer i( i' ,he ra'>e o)

1%

. The varia,io' o) oil recovery ver((

capillary 'mer i( (ho?' i' Fi>re 1%.

8/11/2019 Jpst 2014 Vol. 4 No. 1






6?

3igure 10, eco!ery !ersus capillary num$er

CONCLUSIONS

The re(l,( (ho? ,ha, i'crea(i'> i'3ec,io' )lo?

ra,e #ecrea(e( )i'al recovery& ?hich co')irm(

,he re(l,( o) previo( ?or(. oreover& a

#ecrea(i'> ,re'# o) oil recovery ?a( vi(ile i'

>la(( micromo#el(. The compari(o' o) ,he

recovery i' ,he horizo',al a'# ver,ical po(i,io'

(ho?( ,ha, ,he recovery o) oil i( hi>her i' ,he

ver,ical mo#e ,ha' ,he horizo',al mo#e& ?hich

ca' e #e ,o >ravi,y #rai'a>e a'# ,he pi(,o'

lie #i(placeme', o) oil y >a( occrri'> i' ,he

ver,ical mo#e. The )ollo?i'> re(l,( o) ,he >a(

i'3ec,io' experime',( a'# ,he a'aly(i( o) >ravi,y

#rai'a>e are achieve#:

1

;il recovery mecha'i(m i' ,he poro(

me#ia ?i,h i'crea(i'> pre((re i( a(ically

ei,her #e ,o ,he #e(irale improveme', i'

vi(co(i,y a'# a re#c,io' i' i',er)acial

,e'(io' or eca(e a' i'crea(e i' )orma,io'

volme )ac,or ha( a (mall e))ec, o' ,he

re(i#al oil (a,ra,io'.

2 , i( expec,e# ,ha, >ravi,y #rai'a>e

#i(placeme', i' ,he ver,ical >a( i'3ec,io'

provi#e( e,,er re(l,( #e ,o )ilm )lo?.

!

=a( i'3ec,io' ca' pro#ce more ,ha' 6%H

o) ,he i'i,ial oil i' place o) ,he re(ervoir(

?i,h lo? permeaili,y& i) ,he re(ervoir

pre((re i( ep, hi>h e'o>h '#er mi'i

mm mi(cile pre((re /P0 y co'

,rolli'> ,he )lo?.

"

, i( expec,e# ,ha, co've',io'al re(ervoir(

?i,h lo? permeaili,y ca' achieve a hi>h oil

recovery )ac,or a, i'3ec,io' ra,e( hi>her

,ha' maximm >ravi,y #rai'a>e.

5

The experime',( o) ,he crre', ?or ?ere

per)orme# o' a (i'>le ma,rix loc& (i'ce

#i(placeme', i' )rac,re# re(ervoir( occr('#er (,ale >ravi,y #rai'a>eD ,h( a hi>h

oil recovery i( expec,e# )rom immi(cile

>a( i'3ec,io' i' lo? permeaili,y )rac,re#

re(ervoir( ep, a, rela,ively hi>h pre((re(.

NOMENCLATURE

A /m20 <ro(( (ec,io' area

"o /lT0 Forma,io' volme )ac,or

g /m(20 =ravi,y accelera,io'

=;R =a( oil ra,io

' /-0 Permeaili,y

' w E))ec,ive permeaili,y o) ?a,er

L /m0 Ke'>,h

Nc <apillary 'mer

P /Pa0 Pre((re #i))ere'ce

q /m!(0 Flo? ra,e

V /m(0 eloci,y

%ree sym$olsϕ Poro(i,y

! /pa.(0 i(co(i,y

σ /*m0 r)ace ,e'(io'

REFERENCES

B1C $l$'azi . -.& OE'ha'ce# ;il Recovery

Tech'iAe( a'# *i,ro>e' '3ec,io'&

(anadian Society of )$*loration +eo

*hy-ici-t- .ecorder & 2009& 28!!.

B2C

ai#i $. .& O=a( '3ec,io' Mill ie ;il

Recovery i' i>h Permeaili,y Re(ervoir(

'#er =ravi,y -rai'a>e&Q Prepare# )or

To,al ;il <o. 1@@1.

B!C oro(h . a'# ai#i $. .& Oer,ical =a(

oil -i(placeme',( i' Ko? Permeaili,y

Ko'> <ore a, -i))ere', Ra,e( a'# Pre((re

elo? P&Q PE paper 5!221&

pre(e',e# a, /)#S i' ahrai'& a'ama&

Ferary 2%2! 1@@@.

B"C

Lazemi .& =ilma' . R.& a'# El(hara?y $.

6"."

61.61

5%.2

"!.!6

"%

5%

6%

%

%.E+%% 2.E% ".E% 6.E% 8.E%

: l t i m a t e

e c o ! e r y . 4 /

N c

8/11/2019 Jpst 2014 Vol. 4 No. 1





6@

.& O$'aly,ical a'# *merical ol,io' o)

;il Recovery )rom Frac,re# Re(ervoir(

?i,h Empirical Tra'()er F'c,io'(&Q SP)

.e-er0oir )ngineering& ay 1@@2.

B5C ohamma#i .& Lharra, R.& Lhalili .& a'#

ehra')ar .& O;p,imal <o'#i,io'( )ormmi(cile Recycle =a( '3ec,io' Proce((:

$ imla,io' ,#y )or ;'e o) ,he ra'ia'

;il Re(ervoir(&Q Scientia1ranica, Tran-

action- (2 (hemi-try and (hemical )ngi

neering 34& 2011& 1"%1"11.

B6C

a>hi>h. . S. .& a'# Gor,(o( G. <.&

Oi(aliza,io' a'# imla,io' o) mmi(

cile -i(placeme', i' Frac,re# y(,em

7(i'> icro mo#el(: .-rai'a>e&Q Journal

of (olloid and 1nterface Science 355& 1@@4&

16819.

BC oro(h . a'# ai#i $. .& Oer,ical =a(

oil -i(placeme',( i' Ko? Permeaili,yKo'> <ore a, -i))ere', Ra,e( a'# Pre((re

elo? P&Q PE paper 5!221&

pre(e',e# a, /)#S i' ahrai'& a'ama&

Ferary 2%2! 1@@@.

8/11/2019 Jpst 2014 Vol. 4 No. 1




Mohammad Reza Jafari Nasr


Tel: +98 214 82 !21

"a#:+98 21 44$! 94%

Article history

Re&ei'ed: Mar&h %2( 2%1!

Re&ei'ed in re'ised form: J)ne 2!( 2%1!

*&&eped: J)l, 1!( 2%1!

*'aila-le online: Mar&h 1%( 2%14

Journal of Petroleum Science and Technology 2014 , 41/( $%081 hp:jps.ripi.ir

2%14 Resear&h 3nsi)e of erole)m 3nd)sr, R33/

70

AN OPTIMIZATION APPROACH TO REFINERY STEAM

MANAGEMENT WITH CONSIDERATION OF CO2 EMISSION

ohammad !e"a Jafari #asr1*$ a%id Amidpour2$ and &assan 'hodaei2

1 Resear&h 3nsi)e of erole)m 3nd)sr, R33/( Tehran( 3ran

2 5eparmen of Me&hani&al En6ineerin6( 7. N. Toosi ni'ersi, of Te&hnolo6,( Tehran( 3ran

ABSTRACT

The imporan&e of ener6, &risis and 6lo-al armin6 ne&essiaes presenin6 srae6ies in order o

de&rease he amo)n of emissions as ell as f)el &ons)mpion in lar6e and &omple# ind)sries s)&h

as refineries and pero&hemi&al ind)sries. enerall,( refiner, seam neor;s are re6arded as

)nis hi&h &ons)me f)el enormo)sl,. 3n his paper( he seam neor; of Tehran <il Refiner, is

&onsidered as an ind)srial &ase s)d,. Then( 'ario)s s&enarios are proposed o modif, he

neor;. 3n his re6ard( he neor; and s)66esed s&enarios are iniiall, modeled ino =T*R

sofare en'ironmen. Ne#( he, are sim)laed o esimae pro&ess parameers and &oss.

*ferards( ea&h s&enario is separael, opimized and( afer &omparison( he -es s&enario is

&hosen from he 'iepoin of oal ann)alized &os T*>/. The o-je&i'e f)n&ion of opimizaion is

o minimize T*>. * he se&ond sa6e( he amo)n of &ar-on dio#ide prod)&ion is &al&)laed for all

he proposed s&enarios( -efore and afer opimizaion. 3n addiion( he a# of prod)&ion 7,oo

roo&ol/ is added o he T*> of ea&h s&enario. =in&e in his 'ersion of =T*R sofare( he effe&s of

><2 emission ha'e no -een a;en ino a&&o)n( a &om-inaion of he res)ls of T*> in he sofare

&onsiderin6 ><2 and is effe& on T*> has -een &onsidered as a ne in'esi6aion. 3n fa&( -ohe&onomi&al and en'ironmenal iss)es are a;en ino a&&o)n. Moreo'er( he s&enarios are

sim)laneo)sl, &ompared ih ea&h oher and he -es s&enario is &hosen ih &onsiderin6 &ar-on

dio#ide a#es.

'ey(ords: Rerofi( =eam Neor;s( ><2( E&onom,( <pimizaion

INTRODUCTION

Refiner, seam neor; is &onsidered as a )ni

ha 6real, &ons)mes ener6,. The main

o-je&i'e of he neor; is o prod)&e he

seam( hi&h is re?)ired in differen sie

pro&esses. The amo)n of f)el &ons)mpion in

seam neor;s is enormo)sl, hi6h -e&a)se of

-oilers and oher f)el0&ons)min6 &omponens.

")rhermore( aer &ons)mpion and reamen

&oss as ell as mainenan&e &os ha'e &a)sed

he amo)n of oal operain6 &os o in&rease.

en&e( he red)&ion of ener6, &ons)mpion

si6nifi&anl, sa'es oal operain6 &oss. 3n

addiion( i is possi-le o red)&e oal ann)alized

&os hro)6h inrod)&in6 ne s&enarios( hi&h

impro'e he neor; performan&e.

5ifferen approa&hes are proposed o opimize

seam neor;s( hi&h &an -e &ae6orized as:

8/11/2019 Jpst 2014 Vol. 4 No. 1


*n <pimizaion *pproa&h o Refin

Journal of Petroleum Science and T

2%14 Resear&h 3nsi)e of erol

1/ )sin6 renea-le ener6,A 2

performan&e of he neor;

sellin6 or -),in6 he poe

impored( hi&h depends on p

6raphi&al srae6ies of &o)n

&o)plin6 -eeen he neor

poer plansA / )sin6 hea

6enerain6 s,sems and 6as )r

old -oilers and so on. "i6)r

oppor)niies of opimizaion

or;s.

)igure 1 The opportunities of opti

net(or+s

MODELING

The m)lidis&iplinar, desi6n

s,sem neor;s in lar6e and &o

plans s)&h as oil refiner, and

has -een inrod)&ed -, =mih

e al. inrod)&ed a &on&ep

operaion of ind)srial seam )

in6 s)persr)&)re models( hi&

as a main so)r&e of =T*R

opimizaion e&hni?)es are sima mi#ed ine6er linear pro6ram

m)laion in his sofare B2(!C.

)sed 6rand &omposie &)r'es in

he idea of he le'el anal,sis of

B4C. ")rher in'esi6aions s)

=mih e al. are also in&l)d

impro'e he sofare imp

ind)srial &ase s)dies B(FC.

sill some la&; of daa in erms

his paper( -, &onsiderin6 Teh

r, G S

chnology 2014( 41/( $%081

e)m 3nd)sr, R33/

/ promoin6 he

omponensA !/

r e#pored or

olii&al and 6eo0

riesA 4/ seam

s and adja&en

re&o'er, seam

-ines insead of

1 shos he

in seam ne0

mi"ation in steam

opimizaion of

mple# ind)srial

pero&hemi&als

B1C. Ma'romais

al desi6n and

r-ines &onsider0

h had -een )sed

sofare. The

pl, fa&iliaed -,in6 M3D/ for0

ara-ano' e al.

order o e#end

seam neor;s

h as hose -,

d in order o

lemenaion in

e'er( here is

of emissions. 3n

ran <il Refiner,

seam neor; as a real &as

ha'e -een inrod)&ed in

minim)m oal ann)alize &

s)&h as ,pe of f)el &ons)

)r-ine flo raes( and h

re?)ired and prod)&ed in d

ell as he f)el pri&es ere

he sofare B$(8C. ")rher

of he red)&ion of ><2 e

neor; de'i&es )sed -,

applied o differen si# s

&onsider emission and i

ann)alized &osA hoe'er(

an&e of emission( here is

a&&)rae models in &onj)n&of he sim)laion.

STAR Software Packag

=T*R is a sofare pa&;a6e

)ili, and &o6eneraion

a&ions -eeen he pro&e

he seam s,sem( seam

ih a)#iliar, firin6 opion

fired heaers( and &ooli

anal,zed )sin6 =T*R pa&;a

red)&in6 ener6, &oss or pl

in'esmen in si)aions

operaions on he sie are

e?)ipmen needs o -e

effe&i'e &apial in'esme

in'esi6aed. =T*R pa&;a6e

in'esi6ae he red)&ion

o mee i6her en'ironm

sim)laion of seam neRefiner, &onsiderin6 diff

-een performed -, )sin

a&hie'e he minim)m oa

addiion( an esimaion of

is effe& on oal ann)ali

in'esi6aed B8C.

3n his re6ard( he seam n

Refiner, norhern sie/ ha

an ind)srial &ase s)d,. He

old( he amo)n of f)el is a

Journal of Petroleumcience and Technology

hp:jps.ripi.ir

, 71

e s)d,( si# s&enarios

rder o a&hie'e he

os. 7e, informaion

ed -, -oilers( seam

e amo)n of seam

ifferen pro&esses as

)sed as inp) daa in

more( an esimaion

issions from seam

adalla e al. B9C( is

enarios in order o

s effe& on oal

d)e o he impor0

a need o )se more

ion ih he res)ls

for he desi6n of sie

s,sems. The iner0

sses on he sie and

r-ines( 6as )r-ines

/( -oiler ho)se( lo&al

6 s,sems are all

e. 3 &an -e )sed for

nnin6 infrasr)&)re

here &han6es o

ni&ipaed or ener6,

repla&ed. The mos

n srae6, &an -e

&an also -e )sed o

f fl)e 6as emissions

enal re6)laions. *

or; in Tehran <ilren s&enarios has

=T*R in order o

l ann)alized &osA in

><2 prod)&ion and

zed &os ha'e -een

or; of Tehran <il

-een &onsidered as

&a)se he neor; is

a hi6h &ons)mpion

8/11/2019 Jpst 2014 Vol. 4 No. 1



Science and Technology M. R. Jafari Nasr( M. *midpo)r( and . 7hodaei

Journal of Petroleum Science and Technology 2014( 41/( $%081 hp:jps.ripi.ir


72 ,

le'el. *ddiionall,( sin&e he -oilers ha'e no

e&onomizer( heir e#ha)s empera)re is hi6h

and heir effi&ien&, is lo. These fa&ors &an

&onse?)enl, in&rease he amo)n of air

poll)ions espe&iall, ><2. The neor;s areshon in "i6)re 2 B8(9C. The neor; &onsiss of

-oilers( seam and pro&ess )r-ines( de0aeraor(

seam main headers a hree le'els( hi&h are

( M( and D( and o ho and &old &onden0

sae headers. The fra&ion of f)el &ons)mpion

in -oilers is 6enerall, % per&en na)ral 6as and

% per&en f)el oil.

Correlations and Models

Boilers

The &orrelaions of -oiler effi&ien&, and

-lodon sream ha'e -een menioned -elo

B1C.

( )

1 Max

M Efficiency

B M AM =

+ + 1/

here( M represens seam mass floA MMax is

ma#im)m seam mass flo and * and H sand

for he &oeffi&iens of -oiler effi&ien&,

AI %.%12F( B I %.21F/.

The amo)n of -oiler effi&ien&, is esimaed

hro)6h a re6ression anal,sis. The anal,sis

implemens hermod,nami& parameers s)&h as

empera)re and sa)raed empera)re( pres0

s)re( and he enhalp, of he seam s)pplied for

header as ell as he mass flo rae of he

seam prod)&ed in he -oilerA hen( i plos he

effi&ien&, of he -oiler 'ers)s he mass flo rae

of he prod)&ed seam. "i6)re ! represens he

relaionship -eeen he effi&ien&, of -oiler and

he mass flo rae of he seam prod)&ed.

)igure - .fficiency of the /oilers ersus the mass

flo( rate of the steam produced

)igure 2 The steam net(or+ of Tehran oil refinery #orthern site 310

8/11/2019 Jpst 2014 Vol. 4 No. 1


Journal of Petroleum*n <pimizaion *pproa&h o Refiner, G Science and Technology



, 7-

Steam Turbine

The &orrelaions ha &al&)lae shafor; and

he effi&ien&, of seam )r-ines( hi&h ere

iniiall, inrod)&ed -, Ma'romanis B2(!C( are

menioned -elo.

( ) ( )( )

max

max max max

1

1 1

is

willan

AW H

m

m m m

η

η η

= ∆ −

− − − −

2/

( )

max

maxmax

11

.

1 1 .

is

willan

A

B H m

m

m

η η

η

= −

∆

− −

!/

max

max

willanloss

W

W W η =

+

4/

here( W is shafor;A m represens seam flo

rae and W loss is inernal losses. A and B are

&al&)laed as 6i'en -, B!C:

0.00423 Sat A T = × ∆ /

=1.155+ 0.000538 TSat B × ∆ F/

3n he poer re6ression se&ion( i is possi-le o

esimae effi&ien&,( shafor;( o)le empera0

)re e&. )sin6 header empera)re and

sa)raed empera)re as ell as seam )r-ine

flo rae. "i6)re 4 represens he relaionship

-eeen he shafpoer of )r-ine and is mass

flo rae.

)igure 4 Shaftpo(er of steam tur/ine ersus its

mass flo( rate

Gas Turbine

3n his se&ion( afer spe&if,in6 f)el ,pe and he

shafpoer of 6as )r-ine( he sofare pa&;a6e

deermines e#ha)s empera)re( mass flo

rae( and hea load as ell as f)el &ons)mpionand &apial &os. "i6)re shos he relaionship

-eeen he effi&ien&, of 6as )r-ine and is

shafpoer.

)igure 5 .fficiency of gas tur/ine ersus its shaft

po(er

Scenario Suggestion

erein( differen s&enarios are proposed o

impro'e he neor; as lised in Ta-le 1. The

s&enarios 2 o inrod)&e R= and 6as )r-ine

)nder differen &ondiions. =&enario 1 and F are

he same( -) he f)el raio is % na)ral 6as

and % f)el oil in s&enario 1( hile i is $%

na)ral 6as and !% f)el oil in s&enario F.

enerall,( he f)el raio in he proposed

s&enarios is fi#ed or 'aria-le d)rin6 opimiza0

ion. =in&e s&enarios 2 o inrod)&e ne

e?)ipmen o he neor;( &apial &os m)s -e

added o he oal ann)alized &os. "i6)re Fshos he seam neor; of Tehran <il Refiner,

modified a&&ordin6 o he ne s&enarios 20/.

The &oss of f)els are -ased on he ersian )lf

zone &oss( as lised in Ta-le 2 B4C.

Simulation of Tehran Oil Refinery Steam

Network

*fer presenin6 he s&enarios( he seam ne0

or; is sim)laed in =T*R sofare en'iron0

men. The sim)laion res)ls s)&h as oal

8/11/2019 Jpst 2014 Vol. 4 No. 1






74 ,

ann)alized &os( f)el hea load of all pro&esses

and e?)ipmen as ell as )n)sed hea load ill

-e applied o he opimizaion phase. "i6)re $

shos he sim)laion of he s&enario 1 and F.

"i6)re 8 ill)sraes he s&enarios 2 o sim)0laed -, =T*R sofare pa&;a6e.

Ta/le 2 Cost of fuels /ased on the Persian 6ulf "one

costs 34

Type of )uel Costs

")el <il Kon/ !48.24 Kon/

Na)ral as Kon/ 2%9.2%4 Kon/

3mpored oer K;Lh/ %.%F K;Lh/

Optimization of Tehran Oil Refinery Steam

Network

Dar6e and &omple# )ili, s,sems ofen ha'e

si6nifi&an s&ope for opimizaion B1C. The

o-je&i'e f)n&ion of opimizaion is o minimize

oal ann)alized &oss. =ome parameers &an -e

limied d)rin6 he opimizaion s)&h as 6as

)r-ine poer( he amo)n of he seam

prod)&ed in R=( and f)el raio. The opimiza0ion approa&h is -ased )pon fi#ed header

&ondiions s)&h as empera)re and press)re.

The seam s,sem model is firs sim)laed and

he press)res and empera)res of he seam

main is remained fi#ed. The model is hen

opimized )sin6 a linear pro6ram ih he

empera)res of he mains remainin6 fi#ed. The

re0sim)laion of he model hen allos he

empera)re of he seam mains o -e

deermined.

Ta/le 1 The scenarios proposed to modify the steam net(or+

)uel !atio Steam

Tur/ine

6as

Tur/ine &!S6oiler 4 oiler - oiler 2 oiler 1 Scenario

ar. %0%/ - - 1 .8ist

"i#ed 2

aria-le -

"i#ed 4

aria-le 5

ar. $%0!%/ - - 9

)igure 9 The steam net(or+ of Tehran :il !efinery modified according to the ne( scenarios 2;5 310

8/11/2019 Jpst 2014 Vol. 4 No. 1


8/11/2019 Jpst 2014 Vol. 4 No. 1



Science and Technology

Journal of Petroleum Science and T

2%14 Resear&h 3nsi)e of erol

79 ,

Analysis of Tehran Oil R

Network Considering CO2 E

>ar-on dio#ide as a 6reenho)se

role in 6lo-al armin6. =)dies

responsi-le for a-o) o0hi

han&ed 6reenho)se effe&. 3n o

en'ironmenal sandards as a6r

roo&ol( he &hemi&al ind)srie

o red)&e heir 6reenho)se

pari&)lar ><2 emissions B$(9C.

&ar-on dio#ide prod)&in6 so

neor;s. 3n his se&ion( he

he e#isin6 &ase and he propo

-oh sim)laion and opimiz

anal,zed from he 'iepoin

The f)el is &om-)sed hen

prod)&in6 ><2 a&&ordin6 o foll

eri& rea&ion B$C:

2 24 2

x y

y yC H x O xCO

+ + → +

here( x and y denoe he n)m

and h,dro6en / aoms respe&

)igure = Sources producing car/on

M. R. Jafari Nasr( M. *m

chnology 2014( 41/( $%081

e)m 3nd)sr, R33/

finery Steam

mission

6as pla,s a 'ial

sho ha i is

rds of he en0

der o mee he

ed in he 7,oo

s are &hallen6ed

emissions( in

"i6)re 9 shos

r&es in seam

seam neor;

sed s&enarios/ in

ion saes( is

f ><2 emission.

mi#ed ih air(

in6 soi&hiom0

2 H O

$/

er of &ar-on >/

i'el, presen in

he f)el &omposiionsA he &

&ar-on is ass)med.

The amo)n of he ><2 e

a&&ordin6 o he folloin6 e

2

%

100

fuelCO

Q C M

NHV α

=

here( e?)al o !.F$/ i

masses of ><2 and >A N

ne heain6 'al)e of a f)el

of > dimensionless/ B$(8C.

Ta-le ! represens he ne

f)el &ons)med o6eher

There are o approa&heshe firs is o )se sim)lai

res)ls. The se&ond appro

he folloin6 form)las B$C:

*. ><2 Emission for =eam H

( )

Process

Process

07862

Fuel

FTBProcess

FTB S tak e

QQ

T T h

T T

λ = ×

−− ×

−

dio8ide in steam net(or+s 31$10$11

idpo)r( and . 7hodaei

hp:jps.ripi.ir

omplee o#idaion of

mied is &al&)laed

?)aion:

8/

s he raio of molar

;J;6/ represens he

ih a &ar-on &onen

heain6 'al)e of he

ih &ar-on &onen.

o &omp)in6 QFuel Aon and opimizaion

&h is o implemen

oilers

9/

8/11/2019 Jpst 2014 Vol. 4 No. 1





, 77

here( λProcess ;J;6/ and hProcess ;J;6/ are he

laen hea and enhalp, of seam deli'ered o

he pro&ess respe&i'el,A T"TH >/ is he flame

empera)re of he -oiler fl)e 6ases.

Ta/le - >ata for heating fuels to determine C:2 emissions 39;11

Car/on ?#&@ +J+g

8F. 4%24)uel oil

$.4 4F11 #atural gas

H. ><2 Emission for as T)r-ines

Process 1

1Fuel

GT c

QQ

η η =

−

1%/

here( QProcess is he amo)n of f)el -)rnA !T

represens he effi&ien&, of a 6as )r-ine

dimensionless/ and c sands for he >arno

fa&or dimensionless/.

273

inlet outlet C

inlet

T T

T η

−=

+

11/

here( T inlet >/ is he empera)re a he inle

of he 6as )r-ine &om-)sion empera)re/

and T outlet >/ is he empera)re a he o)le of

he 6as )r-ine fl)e 6as empera)re/.

, ,Fuel HRSG Fuel Gas Turbine

Fuel , Supplimrntry Firing

Q Q

Q

= +

12/


Simulation and Optimization Results

without Considering CO2 Tax

The sim)laion and opimizaion res)ls in

differen s&enarios are lised in Ta-le 4. The

differen&e -eeen he oal ann)alized &os of

differen &ases in he -ase and opim)m saes

are shon in "i6)re 1%. 3n s&enario ( he

deferen&e -eeen T*> in he sim)laion and

opimizaion saes is 6reaer han he ohers&enarios. 3n fa&( he opim)m sae of s&enario

is he -es from he 'iepoin of T*>. "i6)re

11 shos he amo)n of f)el &ons)mpion in he

proposed s&enarios in -oh sim)laion and

opimizaion saes. Ta-les and F sho he

oal amo)n of seam prod)&ion on per ho)r/

in differen s&enarios in -oh sim)laion and

opimizaion s&enarios.

Ta/le 4 Simulation and optimi"ation results of different scenarios

Total Annuali"ed Cost Byr

>ifferences:ptimumaseScenario

0%.98%%2×1%$ %.4$4F$$×1%

8 %.$2$2$×1%

8 1 .8ist

0%.!4%FF!×1%$ %.F1298F×1%

8 %.F4$%2×1%

8 2

0%.$%2188×1%$ %.4F8$2×1%

8 %.!8$91×1%

8 -

0%.1292F×1%8 %.4!1%$1×1%

8 %.F99F×1%

8 4

0%.1F42%×1%8 %.!91$$×1%

8 %.F99F×1%

8 5

0%.!944!1×1%$ %.4$4F$$×1%

8 %.1412%×1%

8 9

)igure 10 >ifference /et(een the total annuali"ed cost of the proposed scenarios in the /ase and optimum

states

8/11/2019 Jpst 2014 Vol. 4 No. 1






7< ,

)igure 11 The amount of fuel consumption in the proposed scenarios in /oth simulation and optimi"ation

states

Ta/le 5 The amount of steam production in different scenarios simulation state

odel 9 odel 5 odel 4 odel - odel 2 odel 1 odel

FF.F %%% % FF.F oiler 1

FF.FFF.FFF.FFF.F8 FF.Foiler 2

FF.F%%%% FF.Foiler -

FF.FFF.FFF.FFF.F8F FF.Foiler 4

% 1!!.4 1!!.4 1!!.4 12% % &!S6

2FF.F2FF.F2FF.F2FF.F 291 2FF.4 Total

Ta/le 9 The amount of steam production in different scenarios optimi"ation state

odel 9 odel 5 odel 4 odel - odel 2 odel 1 odel 12 %%%%12 oiler 1

F2.%44 F4.FF9 F4.FF9 1%.FF !%.FF9 F2.%44 oiler 2

% %%%%% oiler -

12 %%121212oiler 4

% 14% 14% 14% 12% % &!S6

!12.%44 2%4.FF9 2%4.FF9 2$.FF 2$.F9 !12.%4 Total

Ta/le 7 Simulation and optimi"ation results in different scenarios considering C:2 ta8

Total Annuali"ed Cost (ith C:2 Ta8 Byr

Scenario ase :ptimum

1 .8ist F!.912×1%8 2.8%×1%

8

2 $1.84F×1%8 F$.F%2×1%

8

- F%.412×1%8 1.14F×1%

8

4 F2.1%×1%8 4$.F×1%

8

5 F2.1%×1%8 42.F11×1%

8

9 F.!%%×1%8 2.8%×1%

8

8/11/2019 Jpst 2014 Vol. 4 No. 1





, 7=

Ta/le < The amount of C:2 produced in different scenarios in /oth simulation and optimi"ation state

tonhr

Scenario ase :ptimum

1 .8ist %.! !8.91

2 4.!4 4$.9$

- 49.8 !2.F4

4 1.8! !!.8F

5 1.8! 2F.28

9 !$.% !8.91

)igure 12 Total annuali"ed cost of the proposed scenarios after simulation

)igure 1- Total annuali"ed cost of the proposed scenarios after optimi"ation

*s shon in "i6)re 11( he na)ral 6as &ons)mp0

ion is in&reased in he opim)m sae of he

e#isin6 &ase. 3 sho)ld -e ;ep in mind ha he

f)el raio in he e#isin6 &ase is 1%% na)ral 6as.

3 is a&&epa-le -e&a)se T*> ih and iho)/

><2 a# and prod)&ion are si6nifi&anl, red)&ed(

alho)6h he na)ral 6as &ons)mpion is o-'i0

o)sl, in&reased d)rin6 opimizaion.

Simulation and Optimization Results with

Considering CO2 Tax

*fer &al&)lain6 he amo)n of ><2 prod)&ion

for he &omponens of Tehran <il Refiner,

seam neor;( oal ann)alized &os &onsider0

in6 ><2 prod)&ion a# is &al&)laed for all he

proposed s&enarios in -oh sim)laion and

opimizaion saes as shon in Ta-le $ B$(1%(

12C. 3n addiion( he amo)ns of ><2 prod)&ion

8/11/2019 Jpst 2014 Vol. 4 No. 1






<0 ,

are shon in Ta-le $. Ta-les $ and 8 sho ha

s&enario ( hi&h has -een opimized( is he

-es s&enario from he 'iepoin of ><2 prod)&0

ion as ell as T*> &onsiderin6 ><2 a#.

"inall,( he &omparison -eeen he res)ls

o-ained from he sim)laion and opimizaion

in differen s&enarios ih and iho) ><2 a#/

is shon in "i6)res 12 and 1!. The res)ls of he

sim)laion "i6)re 12/ and he opimizaion

"i6)re 1!/ indi&ae ha he amo)n of T*> ih

and iho) ><2 a# is dramai&all, red)&ed

afer opimizaion in all he proposed s&enarios.

=&enario is he -es from he 'iepoin of T*>

ih and iho) ><2 a#/.

CONCLUSIONS

*fer he sim)laion and opimizaion of Tehran

<il Refiner, seam neor;( he folloin6

res)ls ere o-ained for he proposed s&e0

narios. =&enario as sele&ed as he -es0

opimized s&enario. *fer ha( he opimized

res)ls of s&enario ere &ompared ih he

presen seam neor;. The &omparison

shoed ha he amo)n of T*> as red)&ed -,

!1( iho) &onsiderin6 &ar-on dio#ide a#. 3n

addiion( hen he &ar-on dio#ide a# as a;en

ino a&&o)n( he amo)n of T*> as de&reased

-, !!. Hesides( s&enario remar;a-l, red)&ed

he amo)n of &ar-on dio#ide prod)&ion -,

9$ in &omparison ih he e#isin6 neor;.

Therefore( i as ded)&ed ha s&enario as

feasi-l, he -es proposed s&enario from he

'iepoin of T*> as ell as he amo)n of

6reenho)se 6as emissions.

NOMENCLATURE

><N5 >ondensin6 header

T as )r-ine

H"L =pe&ifi& enhalp, of -oiler

feed aer

>R =pe&ifi& enhalp, of

&ondensae rae

i6h press)re seam

R= ea re&o'er, seam

6eneraor

=TE*M =pe&ifi& enhalp, of seam

ENT =pe&ifi& enhalp, of seam

'enedTL =pe&ifi& enhalp, of reaed

aer

D Do press)re seam

M Mass flo rae

MH"L Hoiler feed aer flo rae

M>R =eam &ondensae flo rae

M Medi)m press)re seam

M=TE*M =eam flo rae

MTL Treaed aer flo rae

O ea load

6ree+ Sym/ols

roporion of deareaion

seam raed

c >arno fa&or effi&ien&,

REFERENCES

B1C =mih R.( "hemical Process #esign and

$ntegration( The *ri)m( =o)hern ae(

>hi&heser( Les =)sse# <19 8=O(

En6land: John Lile, P =ons Dd.( 2005(4FF.

B2C Ma'romais =. .( Q>on&ep)al 5esi6n and

<peraion of 3nd)srial =eam T)r-ines

Neor;s( Ph%#% Thesis( M3=T( 7( 1==9.

B!C Ma'romais =. . and 7o;ossis *. >.(

Q>hemi&al En6ineerin6 =&ien&e( >on&ep0

)al <pimizaion of ili, Neor;s for

<peraional ariaions: ar 33. Neor;

5e'elopmen and <pimizaion(

"hemical &ngineering Science, 1==< , '(, 8 ,

1801F%8%

B4C ar-ano' . =.( err, =. J.( Ma;ana S.( )

U. U.( and =mih R.( QTop De'el *nal,sis of

ili, =,sems( Trans% $"hem& ( 2004(

*)*( $840$9!.

BC =T*R =ofare( ersion 2( >ener for

ro&ess 3ne6raion( =&hool of >hemi&al

En6ineerin6 P *nal,i&al =&ien&e( ni'er0

si, of Man&heser( 7( 200=.

BFC =mih R.( *6)ilar <.( err, =.( and Jin07);

7.( Q5e'elopmens in he 5esi6n and <pi0

8/11/2019 Jpst 2014 Vol. 4 No. 1





, <1

mizaion of ili, =,sems( Trans%

$"hem& ( 2007( A)'( 1149011F8.

B$C ,dro&ar-on Halan&e( 3nsi)e for

3nernaional Ener6, =)dies 33E=/( Te&hni0

&al Repor( 3slami& Rep)-li& of 3ran( 2009.

B8C Jafari Nasr M. R.( 7hosh6ofar M. .(*midpo)r M.( QRed)&ion of ><2 Emission

in 3sfehan >r)de <il Refiner, ih ea

3ne6raion( presened a *nd

$nternation+

al "onferences in Modeling, Simulation

and Alied -timi.ation( The erole)m

3nsi)e( *-) 5ha-i( *E( 2007.

B9C adalla M.( <l)ji& .( Jo-son M.( and

=mih R. QEsimaion and Red)&ion of

><2 Emissions from >r)de <il 5isillaion

nis( &nergy ( 2007( **( 1!201!9.

B1%C 7hodaei J. *. .( Q=im)laion and <pi0

mizaion of =eam Neor; in Tehran <il

Refiner,( M%S% Thesis( 7. N. Toosi ni'er0

si, of Te&hnolo6, and he ni'ersi, of

Man&heser( 7( 200<.

B11C 7hosh6ofar Manesh M. .( 7hodaei J. *.(

.( and *midpo)r M.( Q<pimizaion of

=eam Neor; in Tehran <il Refiner,Ne =&enarios/( presened a (/

th $nter+

national "onference of $ndustrial &nergy

&ngineering 0$&T"1( Te#as( =*( 200<.

B12C Jafari Nasr M. R. and 7hodaei J. *. .( Q><2

Red)&ion hro)6h <pimizaion of =eam

Neor; in erole)m Refineries: E'al)a0

ion of Ne =&enario( presened a (/th

$nternational "onference of $ndustrial &n+

ergy &ngineering 0$&T"1( Te#as( =*( 200<.

8/11/2019 Jpst 2014 Vol. 4 No. 1


JOURNAL OF PETROLEUM

SCIENCE AND TECHNOLOGY

Vol. 4, No. 1, 2014

ISSN: 2251-659X

Author Index

Ahmadi, M. 20

Ahmadjo, S. 20

Amidpour, M.70

Arabi, H. 20

Arabian, D. 29

Chao, L. 01

Chengfu, L. 01

Farhadi, F. 29

ha!emi "ejad, #. $1

ong%heng, &. 01

ui%hao, D. 01

uojun, C. 01

Hemma'i, M. ()

*+apour, -. 9

-afari "a!r, M. /. 70

a!iri, ". 9

hodaei -aaabadi H. 70

Lo'fi, /. ))

Moh!ennia, M. ))

Moaei Dehordi, A. 29

Mor'aa+i S. M. M. 20

"ajafi, H. 29

"ejaba', h. /. 20

"eja'i Moharrami, ". ()

3mid+ar, M. 20

4ar+ii, /. $1

/a!hidi, A. M. ))

Shadde, S. ()

Sheng, &. 01

&amanian, #. ()

&ohuri, h. H. 20

8/11/2019 Jpst 2014 Vol. 4 No. 1


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References

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"#$%, 440FEED.

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Example: @randli @., &ue 9., &ic( M., B#ngineering !ames and 'oncepts,C presented at the "nd Int. Conf.

Engineering Education, 7ran(furt, =ermany, "###.

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