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Laboratoire Catalyse & Spectrochimie

Laboratory Catalysis & Spectrochemistry


ENSICAEN, Universit de Caen, CNRS
6 bd du Marchal Juin, 1400 Caen, !rance
http:/www-lcs.ensicaen.fr
Jean-Pierre GILSON
Tl.: 02.31.45.28.15 email: jean-pierre.gilson@ensicaen.fr
Procds Catalytiques en
Raffinage Ptrolier
Buts & Plan du Cours
"ue Int#re $Economie, oli!i"#e, En$ironnemen!, %&imie, Catalyse, 'nie %&imi"#e, (%
d&un se#'ent de l&industrie $chi'i(ue% ) )e#ls cer!ains process#s ca!al*!i"#es seron! +isc#!s
S'inaires si'ilaires * une $in%+,r'ati,n industrielle
-,siti,n du -r,bl.'e/ Envir,nne'ent de l&Industrie -tr,li.re
Une Ra++inerie / 0es ,utils
0es 1rands 2r,cds / HT, Reforming, Isomrisation, FCC
+
, HCK,
Carburants Classi(ues / Essence 3 4iesel
Car!"rants #e Remplacement $ %ro!l&me #e l'H
(
)Raffinerie*
R+rences /
Le Raffinage du Ptrole $ ",lu'es, 156 rec,''ands%, J)- 7au(uier, 8echni2, -aris 1994
5
The Quest, 4: ;er#in, -en#uin, <011
Energy at the Crossroads, ": S'il, MI8 -ress, <00
=l,# de ": S'il $>>>:vaclavs'il:c,'%
Sites de -tr,liers/ +% $>>>:b2:c,'avec Ener#? @utl,,A <060%, ,--on.o!il
$htt2/BB>>>:eCC,n',bil:c,' ?Bc 8he @utl,,A +,r Ener#?/ A "ie> t, <040%, /hell $>>>:shell:c,'?B
Scnari,s% , 8,tal $>>>:t,tal:c,'% 3
-an,ra'a de I!-EN $htt2/BB>>>:i+2ener#iesn,uvelles:c,'B2ublicati,nsBn,tes)de)s?nthese)
2an,ra'aB2an,ra'a)<01<%
@SDA 8echnical Manual, Cha2ter < $htt2/BB>>>:,sha:#,vBdtsB,staB,t'B,t'EivB,t'EivE<:ht'l%
PROCAT 3A, jpg,2012-13
2
EN!R"NNE#EN$ %E
L&!N%'S$R!E PE$R"L!ERE
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3
Energie sur $erre( )lobalit *
(consommation ~0.5 Z J/an)
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4
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5
Energie( %emande et "ffre
Perspective
,. )mil, 2010
%emande #ondiale en Energie
+Primaire,
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6 )imon -enr*, )&ell, 2011
"ffre Energetique
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7
./0, Energ* /#loo1, 2002
Ptrole Li!uide" #e$teurs Energti!ues Essen$e% &ros'ne ( )iesel"*
Car+urants de $hoi, )ensit Energti!ue" -our de no.+reuses annes
Energies Primaires & Carburants
8
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%ensit des ecteurs Energtiques
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9
3. )!imming, T30, 2002
$ransport & %emande de Ptrole
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10
./0, Energ* /#!loo1, 2002
$echnologies Emergentes( Pntration -
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11
./0, Energ* /#!loo1, 2002
(Energie: e
-
+ Molcules)
Pri. des Carburants +/R,
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12
Pri. des Carburants +E',
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13
0orl# #eman#
0illiar+s +e !ep
4n!erna!ional Energ* 5genc* 2002
Annual Growth
2000 - 2010
+ 1.7 %
+ 2.9 %
+ 1.4 %
+ 1.1 %
+ 1.9 %
+ 3.7 %
1973 1990 2000 2010
Others
renewable
Hydraulic
Nuclear
Coal
Natural Gas
Oil
"il & )as( dominant energy sources in the ne.t decade
This outlook assumes a world GDP annual growth of 3,2 %
%emande #ondiale d&Energie (
Scnarios 2002 (I.E.A)
14
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4n!erna!ional Energ* 5genc* 2002
'tilisation du Ptrole & du )a0
0orl# 1il #eman#
Millions of b/d
0.6 %
0.7 %
1.5 %
3.0 %
2.1 %
Annual Growth
2000 - 2010
1973 1990 2000 2010
Petrochemicals
Non-
Energy use
Fuels
heating
Power station
Transport
0orl# 2as #eman#
Millions of boe/d
Annual Growth
2000 - 2010
+ 4.5 %
+ 2.4 %
+ 2 %
1973 1990 2000 2010
Petrochemicals
Residential
Services
Industry
Power plants
15
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Consommation Energtique
4n!erna!ional Energ* 5genc* 2002
CIS
3.2 toe/capita
Latin /.eri$a
1.2 toe/capita
/sia
0.7 toe/capita
/fri$a
0.6 toe/capita
Euro-e
3.2 toe/capita
North /.eri$a
8.3 toe/capita
0iddle East
2.3 toe/capita
Ja-an% &orea%
/ustralia
4.3 toe/capita
How to give access to basic energy needs in the world
)e1elo-ing $ountries*
F1 G ,+ the >,rl>ide 2,2ulati,n
4 G ,+ the ener#? c,nsu'2ti,n
2orld *
5nn#al Energ* cons#mp!ion per capi!a :
1.6 !on of oil e"#i$alen! per *ear
16
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!ntensit Energtique( 123456778
)&ell, 2005
17
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9orld "il & )as Reser:es
/il an+ 'as 7o#rnal, %e+iga8
@il/ 1000 =b, 40 ti'es current ?earl? 2r,ducti,n
1as/ 1100 =b,e, 6H ti'es current ?earl? 2r,ducti,n
I C,'2etitive c,st ,+ 2r,ducti,n +,r h?dr,carb,ns vs ,ther ener#? s,urces
I 7,rld 2r,ven reserves:
4
CIS
Latin America
Asia-Pacific
Africa
Europe
North America
Middle
East
18
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$rading Ptrole Brut
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19
Total
Produits Ptroliers( %emande
/pec, 2006
20
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$rading Produits Ptroliers
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21
Total
;<%R"C=RB'RES > N"N5
C"NEN$!"NNELS ?
)&ell, 2005
22
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Production "il & )as
Oil producers
16 %
Saudi
Aramco
Autres CPN
Ex-Union sovitique
+ Chine
Autres Cies
hors OCDE
Autres Cies
OCDE
Sonatrach
Petronas
ENI
Exxon
Mobil
Royal
Dutch/Shell
Chevron
Texaco
BP
Conoco
Phillips
Petrobras
NIOC (Iran)
Pemex (Mexique)
PDV (Venezuela)
ADNOC
NOC
KPC
INOC (Irak)
NNPC
I.O.C.
N.O.C.
2001 9 )!a!is!ical :e$ie;, 4< - ro+#c!ion p!roli=re 2001 > 64.5 0?@j
Gas producers
I.O.C.
18%
Exxon
Mobil
Shell
BP
Chevron
Texaco
ENI
Conoco
Phillips
PDV
(Venezuela)
Non OCDE
OCDE
Petronas
Qatar
Petroleum
Pemex
(Mexique)
Pertamina
Saudi
Aramco
ADNOC
NIOC (Irak)
Sonatrach
Gazprom
N.O.C.
23
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Compagnies Etatiques +N"C,
& Pri:es +!"C,
24
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Rser:es( Cible #ou:ante *
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25
'n Pionnier ( #@ Aing ;'BBER$
+Shell & USGS, B > PE=A "!L ?
26
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Pic de Production( 'S
A.). Beffe*es, C -#??er!Ds ea1 E, rince!on 3ni$ersi!* ress F2001G
27
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Pic de Production ( 'S
28
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Pics de Production ( #onde
29
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Pics de Production ( #onde
PREDICTED PEAK IN WORLD OIL PRODUCTION
SOURCE PEAK DATE
F. Bernabe ENI SpA (1998) 2000-2005
C. Campbell and J. Laherrre Petroon!"ltant! (1998) 2000-2010
J. #a$en%&e 'orld (e!o"re! In!t&t"te (199)) 2007-2014
*EC+ Internat&onal Ener,- A,en- (1998) 2010-2020
J. Ed.ard! /n&0er!&t- o1 Colorado2 Bo"lder
(1993)
2020
+oE Ener,- In1ormat&on Adm&n&!trat&on
(1998)
>2020
Source : C. Campbell & J. Laherrre
30
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Capacit non utilise (*)
Production totale
)o#rce : 54E
MbBJ
Brut( Capacit vs. Production
40
45
50
55
60
65
70
75
80
85
1980 1985 1990 1995 2000
!n:estissements /uturs +",
)&ell, 2005
32
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Prdiction du Pri. du Brut --
33
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)&ell
E:olution du Pri. du Brut
34
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9 )!a!is!ical :e$ie;
Long5$erm"il Supply5Ressources &
Production
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35
)c&l#m?erger, 2010
Ptrole > facile ?( CdDE e.trait
36
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Long5$erm)as Supply5Ressources
& Production
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37
)c&l#m?erger, 2010
Changement Climatique( Complexit
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38
To!al
Emissions de Carbone +C"
6
,
39
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C"
6
& Effet de Serre
)&ell
40
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C"
6
& Effet de Serre ( Les
Responsabilits
41
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0
200
400
600
800
1000
1200
1400
Annes
Etats-Unis
RU
France
Allemagne
Italie
Japon
1970 1980 1990 2001
)o#rce B/E @ E45 2001
t CO
2
par M USD
de PIB (val. 97)
Emissions de C"
6
FP!B
42
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StocGage )ologique des )ES( Potentiel
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43
34 2t C1
(
5(6 of ,missions to (474
8(4 2t C1
(
)#ont 944 2t ,1R C1(*
376 of ,missions to
(474
344-94 444 2t C1
(
(4-744 6 of ,missions to (474
Source: European Commission, primtre Europen
%

d
u

n
i
v
e
a
u

1
9
9
5
CO CO
NO NO
x x
PM PM- -diesel diesel
COV COV
Benzne Benzne
SO SO
2 2
CO CO
2 2
0
20
40
60
80
100
120
140
1990 1995 2000 2005 2010 2015 2020
%

d
u

n
i
v
e
a
u

1
9
9
5
CO CO
NO NO
x x
PM PM- -diesel diesel
COV COV
Benzne Benzne
SO SO
2 2
CO CO
2 2
0
20
40
60
80
100
120
140
1990 1995 2000 2005 2010 2015 2020
CO CO
NO NO
x x
PM PM- -diesel diesel
COV COV
Benzne Benzne
SO SO
2 2
CO CO
2 2
0
20
40
60
80
100
120
140
1990 1995 2000 2005 2010 2015 2020
Tene#r en so#fre +es car?#ran!s ramene H 50 ppm en 2005 e! 10 ppm en!re 2006 e! 200I
Emissions & $ransport Routier( E'
44
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Consommation et Efficacit +=#,
45
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CoHts de Production des Energies
Renou:elables
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46
Rglementations( Carburants
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47
4J
:"antit #e %ro#"its Consomms: .I;I.I/,R <
= iso-:"alit )In#ices #'1ctane $ Ctane*, il fa"t:
Les #aDors +!"C, en 677I ( /inances
48
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/inances( S;ELL +Contexte,
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49
/inances( S;ELL +!s"ltats,
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50
/inances( S;ELL +CAPE#,
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51
/inances( S;ELL +Cash $lo%,
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52
/inances( S;ELL +Strat&ie Aval,
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53
!n:estissements Raffinage +6771587,
Ke 0on+e, 2005
54
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Refinery Capacity =ddition
55
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%penses en Raffinage +'on(e,
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56
Surcapacit en Raffinage *
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Raffinage en /rance
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58
Raffinage en Europe
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et la R&% -
60
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R&% -
61
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Raffinage Ptrolier
/chma Comple-e car ,>ol"tif et Raisons Histori?"es
/tratgie : Rarranger le rapport C/H po"r mettre la @eman#e en %ro#"its
%troliers en a#?"ation a>ec l'1ffre #e +r"ts
A 2ran#es Familles #'1prations :
/parations %hBsi?"es : @istillation, Cristallisation, ,-tractions
Calorisations :
Con>ersions %rofon#es )CracDing, HB#rocracDing, 1ligomrisations, *
CatalBti?"es o" Thermi?"es
Con>ersions lg&res )Isomrisations, CBclisations* CatalBti?"es
Traitements : ,nle>er #es imp"rets )/, ;, .ta"-, * sans to"cher a" reste
Con#itionnement #es %ro#"its po"r la Cente a"- %artic"liers )Car!"rants,
E"!rifiants, * o" In#"striels )+it"mes, Cires, E"!rifiants, *
F##iti>ation
.langes
.
62
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"ffre +Brut, & %emande +Produits,
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H/CG(.4 H/CG9.H
Rapports ;FC de %i:erses Coupes
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Les "utils du Raffinage
65
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Les "utils du Raffinage +1,
66
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To!al
Les Procds du Raffinage
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67
Les "utils du Raffinage +6,
68
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4%%T, 2011
Les #olcules du Raffinage
69
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Schma $ypique de Raffinerie +1,
70
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<. ,ermeiren L 7- 'ilson
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71
Schma $ypique de Raffinerie +6,
Raffinage ( %fis
,fficacit ,nergti?"e #es Installations : C1
(
,
;ormes s"r les Car!"rants $ Com!"sti!les
;o">elles so"rces #'hB#rocar!"res : 2aI, %troles non-
con>entionnels, +iomasse
Pro+l'.es Trans1erses% Nou1elles 0ol$ules O"
F#?"ation Car!"rants J .ote"rs
%erception #e notre in#"strie :
/ocit
Ke"nes 1s3 /ciences $ Techni?"es
%oliti?"e

72
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#oteur ;CC!( /onctionnement
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73
'. Ke#ng, /riginal: 0i!s#?#s&i
43 /d.ission /56 73 Co.-ression /56
83 Co.-ression
9
/56
:3 ; -lus tard
%emande en E' > tire ? par le )"#
74
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To!al
=dquation $echnologie #oteur 5
Lubrifiants 5 Carburants
75
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To!al
alorisation de la Biomasse
,fficacit ,nergti?"e
,ffet C1
(
, empreinte H
(
1L
0ell-to-0heel FnalBsis <

76
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Bio5Energies( $he Big picture C
Ressources
Cultures ddies annuelles et
pluri-annuelles
plantes et herbacs
sylviculture
Co-produits des cultures ddies
pailles et tiges de crales et
olagineux
rsidus forestiers
Autres co-produits et rsidus
industriels
mnagers
autres
Collecte
Transport
Stockage
Pr-
traitement
Technologies de conversion
Voie thermochimique
combustion
pyrolyse
thermolyse
gazification
Valorisation du gaz de synthse:
purification,sparation
procds catalytiques (FT,
MeOH
Voie biologique
ractions enzymatiques
fermentation
distillation, purification
Dbouchs
Energie
chaleur, vapeur
lectricit
Carburants
naphta
essence
jet
distillats
mthanol
thanol
DME
EMHV; EEHV
ETBE
hydrogne
Produits
glycrol
spcialits FT
alcools
autres
Voie olochimique
raffinage chimique et physique
esterification
hydrotraitement
sparation, purification
77
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La Raffinerie du /utur -
78
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To!al
Popularit vs. SuccJs !/P School
79
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%fis Energtiques +R#,( 6747
K
J#!#ris, 2005
80
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/acteurs de Con:ersion
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81
9 )!a!is!ical :e$ie;
Le S & les ;ydrotraitements
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82
Problmatique du S
%rsent #ans to"tes les fractions
,ffet s"r les CatalBse"rs )%t*
Raffinerie )Rformage*
%ots CatalBti?"es
1#e"rs $ Corrosion
Infl"ence s"r les ,missions )@iesel*
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83
Coupes PtroliJres( S & Co@
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84
BR'$S( Prsence de SL N
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85
MStraight5RunN vs. Processed /ractions
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86
;o">ea": 1lfines <
T
ma-
G A74 C
T
ma-
M 774 C
#odes de $raitement
F!sorption par FlDanolamines: H
(
/
Ea>age Ca"sti?"e: Fractions C
A-N
R-S< 9 NaO< R-S-Na 9<
7
O
/weetening )0eroM

*: E%2, ,ssences, Kros&ne


7 C
7
<
=
-S-< 9 > O
7
C
7
<
=
-S-S-C
7
<
=
9<
7
O
H@//HB#rotraitements: Car!"rants
+
<ydrognolyse $atalyti!ue de R-S-< <
7
S
Onit Cla"s: ( H
(
/ + 1
(
( H
(
1 + ( /
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87
;ydrotraitements en Raffinerie
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88
;ydroProcessing
HB#rotraitements: %. change tr&s pe"
HB#rognolBse:
C-/: H@/, C-;: H@;, C-1: H@1, C-.e: H@.
HB#rognation: HP@
1lfines, Fromati?"es
Catalyse 0onofun$tionnelle
HB#rocon>ersions: Con>ersion M 746
HB#roisomrisation: I/1.
HB#rocrac?"age: HCK
Catalyse ?i-fon$tionnelle /$ide 9 0tal"
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89
;istorique ;%S
G98A4: HB#rognation #es Char!ons )Fllemagne*
G9874: Fpplication a" Raffinage %trolier
.oti>ations:
H
(
#isponi!le )Reforming*
F"gmentation #e Q/R #es +r"ts
@eman#e en SProduits ?lan$sT
Rglementations anti-poll"tion
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90
;ydrotraitements( $hemodynamique
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91
%remier %rincipe:
/econ# %rincipe: L
;ydrotraitements( $hemodynamique
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92
,-ception: Li.itation Ther.odyna.i!ue de l@<ydrognation des /ro.ati!ues A
%a!al*se#r Ni0o@5l
2
/
3
,
-2
>20 ?ar, 1000 ppm+e ) +ans ga8ole
BR'$S( ;troatomes & =romatiques
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93
;ydrognolyse en ;%SL ;%N & ;%"
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94
CatalBse"r/ C,M,BAl
<
@
6
, -
D<
K0)100 bar, 8
$ar
K0G c,nv
;%S( Prsence de S MRfractaireN
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95
a* F>ant H@/
!* Fpr&s H@/
#ise en "eu:re 5 ;%S
%aram&tres importants:
RC +,rte'ent eC,ther'i(ues $4'arra#e, @2rati,n 3 ArrLt%
C,ns,''ati,n d&D
<
8?2es de S 3 2rsence d&autres c,'2,ss
CatalBse"rs .onofonctionnels:
Sul+ures MiCtes $'G%/ Ni, C, $<)40% M 7, M, $H)60%
C,'2,siti,n $'G%/ Ni$1)4%, C, $1)4%, M, $F)16%, 7 $1<)1%
Su22,rt/ )Al
<
@
6
C,Nt/ O10G +,ncti,nne'ent
4ure/ ',is)annes
!,r'e/ eCtruds $0it +iCe% M S2h.res $0it =,uill,nant%
Char#e'ent/ haute densit
I'2,rtance du 4'arra#e 3 de l&ArrLt
R#nrati,n 3 Rec?cla#e du Catal?seur
Racte"rs: +$Char#e 3 tauC de c,nversi,n%
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96
=cti:it ;ydrognante de S mi.tes
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97
Charge: Tol"&ne
Conditions* TB8=C C% L<S#B7 h
-4
% P
Tot
BDC +ar% P
<7
B:C +ar
Catalyseurs ;%S( Phases =cti:es
C, * l&,ri#ine de l&activit catal?ti(ue
A l&tat sul+ur, le c,balt est s,us +,r'e de 6 2hases
!euillets de M,S
<
2r,'us
C,
9
S
F
C, / Al
<
@
6
s2inelle
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98
/ites .o
non prom"s
/ites .o prom"s par le Co
)Co.o/*
Etude par !R des catalyseurs +LCS,
"ibrati,ns du C@ en interacti,n avec les 2hases sul+ures
2hases $C@BM,S
<
,u C@BC,M,S%
C1 a#sorption followe# !B IR spectroscopB
C 1
1 C
99
PROCAT 3A, jpg,2012-13
PROCAT 3A, jpg,2012-13
!R de C"( Support K Phases acti:es
?andes de 1i+ration du CO adsor+ sur un Co0oP $ara$trises -ar IR
A
b
s
o
r
b
a
n
c
e
1900 1950 2000 2050 2100 2150 2200
(cm
-1
)
100
Schma d&une unit d&;%S
PROCAT 3A, jpg,2012-13
101
Racteur ;%S( Lit /i.e
PROCAT 3A, jpg,2012-13
102
Racteur ;%S( Ooom
PROCAT 3A, jpg,2012-13
103
Racteur ;%S( Lit /i.e
PROCAT 3A, jpg,2012-13
104
Racteur en Lit Bouillonnant
+;ydrocon:ersion des Rsidus,
PROCAT 3A, jpg,2012-13
105
;%S( Conditions P f +Charge,
PROCAT 3A, jpg,2012-13
106
;%S( Consommation en ;
6
*
PROCAT 3A, jpg,2012-13
107
;%S( %iffusion vs. =cti:it
PROCAT 3A, jpg,2012-13
108
;%S( Empoisonnement par Ni &
PROCAT 3A, jpg,2012-13
109
;%S( )estion du Ni & 5 Porosit
PROCAT 3A, jpg,2012-13
110
;%S( )estion du Ni & B En pratique
PROCAT 3A, jpg,2012-13
111
;%S5# de Rsidus( "ptimisation
PROCAT 3A, jpg,2012-13
112
F: H@. cat alone
+: H@/ cat alone
C: H@. + H@/
E.emple( ;<C"N +Shell,
PROCAT 3A, jpg,2012-13
113
Rgnration de Catalyseurs ;%S
;%S
PROCAT 3A, jpg,2012-13
114
%marrage de Catalyseurs ;%S
PROCAT 3A, jpg,2012-13
115
Potentiel de Nou:eau. Racteurs +1, -
PROCAT 3A, jpg,2012-13
116
/
Fromati?"es
Potentiel de Nou:eau. Racteurs +6, -
PROCAT 3A, jpg,2012-13
117
Potentiel de Nou:eau. Racteurs +8, -
PROCAT 3A, jpg,2012-13
118
Le Rformage Catalytique
PROCAT 3A, jpg,2012-13
119
Le Rformage Catalytique
9. %lace, Histori?"e $ RUle en Raffinerie
(. FnalBse #es Ractions
-r,bl.'es
Racti,ns $8her',d?na'i(ue, * 2r,',uv,ir%
A. CatalBse"r
Cinti(ue
-hases actives
3. @>eloppement #" CatalBse"r
-r,2rits re(uises
-r2arati,n
-r,2rits
R#nrati,n
7. CatalBse"r a" Tra>ail J %roc#
N. Concl"sions $ %erspecti>es
PROCAT 3A, jpg,2012-13
120
PROCAT 3A, jpg,2012-13
121
Position du Reforming
RUle en Raffinage $ Histori?"e
9. /chma #e Raffinage: ) Trai!emen! +# -ea$* Nap&!&a: 4n+ice
+D/c!ane L +# En+ oin! FBis!illa!ionG
PROCAT 3A, jpg,2012-13
122
)JleMi?ili!: fF%on+i!ions opra!oiresG
)Raffinage: 4n+ice +Doc!ane O -
2
Fpo#r -B)(G
)Ptro$hi.ie: 9T.
!ndice+s, d&"ctane( R"N & #"N
PROCAT 3A, jpg,2012-13
123
.ote"r V ,ssence )CBcle 1tto*
)/ensi!ilit: R1; J .1;
)Roa# 1ctane )O/*: )R1; + .1;*/(
;CC! :s@ Essence & %iesel(
en )veloppement* (20+,
-
)
PROCAT 3A, jpg,2012-13
124
DOE, 2006
Rich-Core : SOOT
NO
X
E * ).arrage ( ContrFle 9 CO ( <C 9 Charge le1e
R"N & #"N de diffrentes molcules
PROCAT 3A, jpg,2012-13
125
Charges $ypiques( ;ea:y Naphta
PROCAT 3A, jpg,2012-13
126
#"N de %iffrentes Coupes
PROCAT 3A, jpg,2012-13
127
;istorique du Procd 5 Catalyseurs
98A8: D?dr,+,r'in# $M,@
6
BAl
<
@
6
%
9874: Catal?seurs Cr
<
@
6
BAl
<
@
6
9874: Catal?seurs -tBAl
<
@
6
)Cl $-lat+,r'in#de O1%P%
98N8/ Rhni+,r'in#$-tReBAl
<
@
6
)Cl, -Q 60 bar% 3 -tSnBAl
<
@
6
)Cl $8,tal%
19H1/ 8echn,l,#ie CCR $O1%P%
PROCAT 3A, jpg,2012-13
128
Cla#imir
HF,;/,E
)9893 J (44(*
E* Gni1ersal Oil Produ$ts% )es Plaines% GS/
$hermodynamique( Coupe C
3
PROCAT 3A, jpg,2012-13
129
)Ractions intressantes: ,n#othermi?"es
);om!re #e moles
Con#itions 1pratoires:
T $ %
$hermodynamique(
C.clohexane/ 0en12ne & 3
2
PROCAT 3A, jpg,2012-13
130
Cintique & Effets $hermiques
PROCAT 3A, jpg,2012-13
131
+* Catalyseurs +i-.talli!ues
Ractions & Catalyseur
PROCAT 3A, jpg,2012-13
132
CatalBse"r +i-Fonctionnel:
%t/Fl
(
1
A
-Cl
)%t W @shB#rognation
)Fl
(
1
A
-Cl W Fci#e
Catalyseur( Sensibilit au Na
PROCAT 3A, jpg,2012-13
133
Ractions !ndsirables
PROCAT 3A, jpg,2012-13
134
+enI&ne
)9 6 >ol ma- <*
%ro#"its Eo"r#s
%ro#"its Egers
%ro#"its Egers
@sacti>ation
Effet de la Pression
PROCAT 3A, jpg,2012-13
135
Prparation du Catalyseur( 1@ =l
6
7
8
PROCAT 3A, jpg,2012-13
136
Prparation du Catalyseur(
2. Extr"sion 4 Al
2
5
6
PROCAT 3A, jpg,2012-13
137
X: G( mm
Prparation du Catalyseur(
6."il5%rop4 Al
2
5
6
PROCAT 3A, jpg,2012-13
138
X: G( mm
Catalyseurs Sphriques( "il5%rop
PROCAT 3A, jpg,2012-13
139
Prparation du Catalyseur(
6. A((ition (" Pt & Cl s"r Al
2
5
6
Imprgnation #e Fl
(
1
A
par %t )G4.A-4.H w6*
H
(
%tCl
N
:
Fi-er le %t
3+
s"r Fl
(
1
A
par imprgnation
Chlorer la /"rface #e l'Fl
(
1
A
)G96 Cl* Fci#it
Calciner: G744YC
%? mettre le %t en #ernier lie" L
PROCAT 3A, jpg,2012-13
140
4-
Al
OH
+ PtCl
6
2-
2
Pt Cl Cl
Cl Cl
O O
Al Al
+ 2 HCl
2
Q%tR
Cl
-
) 'eilleure distributi,n du -t
) c,'2titi,n avec -tCl
6
<)
Prparation du Catalyseur(
7. Activation (ans le !acte"r
R#"ction so"s H
(
) H
(
1 $ Frittage*
.o#ration #e l'HB#rognolBse )e-othermi?"e* a" #marrage #e
l'"nit par aZo"t #e / )<*, sa"f s"r %t/n/Fl
(
1
A
-Cl
F##ition contin"e #e Cl )eg3 CCl
3
*, Sdo-eT
PROCAT 3A, jpg,2012-13
141
Prparation du Catalyseur(
,. )sactivation
GA4-74 T charge/Dg catalBse"r s"r 9 cBcle commercial
Classification #e la @sacti>ation:
IRR,C,R/I+E,: Catalyseur H re.-la$er A
.ta"- lo"r#s )%!, Fe, [n, /n, Hg, Fs* affectent les proprits
catalBti?"es #" %t
Chocs thermi?"es affectent la te-t"re )/"rface, Col"me pore"-* #e
l'Fl(1A
R,C,R/I+E,: Catalyseur H Rgnrer A
%t
Frittage ) T + H
(
1 W Taille #e partic"les*: com!"stion #" CoDe <
/: %t + H
(
/ %t/ + H
(
@pUt #e C )CoDe*
\-Fl
(
1
A
%erte #e Cl )H
(
1*
+ases );*
/pcifications:
/ )5 7 J 94ppm*
; )59 ppm*
H
(
1 )53 ppm*
%! + Fs + C" )5(4 pp!*
PROCAT 3A, jpg,2012-13
142
Prparation du Catalyseur(
8. !&nration
IRR,C,RR/I+E,:
@isso"#re le s"pport )Fl
(
1
A
* et rc"prer le %t )Cape-*
R,C,R/I+E,: %rincipes #e +ase
Frr]t #e l'Onit )so"s H
(
, TW(44YC*: dsor+er et r$u-rer les <C
adsor+s
Com!"stion #" CoDe )ai#e #" %t <*: C3= I 73C J O
7
entre 8KC-=CCLC
Resta"rer l'aci#it )Cl*: sous air 9 $o.-os $hlor Cl
7
% CCl
:
% <ClM"
1ers =CCLC
Re#isperser le %t: O,y$hloration
Su$$ession d@ta-es sous <
7
( O
7
H raliser dans l@Gnit A
PROCAT 3A, jpg,2012-13
143
".ychloration( Redispersion du Pt
PROCAT 3A, jpg,2012-13
144
%t
Racteurs pour les Ractions
Contraintes:
Thermo#Bnami?"es
Cinti?"es
imposent le #esign #" Racte"r et les con#itions #'"tilisation
%
Tot
W A J 34 !ar J H
(
/HC W 7-94 J T
>ar
W G744YC
PROCAT 3A, jpg,2012-13
145
f)%* f)T*
Procd( =llure )nrale
PROCAT 3A, jpg,2012-13
146
F: Fo"rs
R: Racte"rs
Racteurs Basse P de Reforming
PROCAT 3A, jpg,2012-13
147
%
%G74 !ar
%5(7 )A* !ar
Racteur Semi5Rgnratif +SRR,
PROCAT 3A, jpg,2012-13
148
Racteur E Rgnration Continue +CCR,
PROCAT 3A, jpg,2012-13
149
$he Continuous Reforming( CCR
PROCAT 3A, jpg,2012-13
150
Ra$teur
-Rdu$teur
-Endother.i!ue
Rgnrateur
)O,ydant
)E,other.i!ue
Transferts
Rgnrateur( #ultifunctions
PROCAT 3A, jpg,2012-13
151
Conditions "pratoires des R.
PROCAT 3A, jpg,2012-13
152
CCR* Rgnration tous les N: Oours
Conditions "pratoires $ypiques
PROCAT 3A, jpg,2012-13
153
+* RON $harge B 8K3=
CCR( Bilans $ypiques
PROCAT 3A, jpg,2012-13
154
=mlioration des Catalyseurs(
mono5 vs. bi5#talliques
T $ CCHW >aria!les opratoires en in#"strie
CFTFEP/,OR/ !i-mtalli?"es )%tRe, %t/n* R,FCT,OR/
%tRe: tr&s sta!le V moBenne-ha"te %, slecti>it moBenne: EIT FI^,
%t/n: tr&s slectif V !asse %, pe" sta!le: EIT .1+IE,
PROCAT 3A, jpg,2012-13
155
Te.-rature
C"NCL'S!"NS
9. +ilan %ositif
%ro#"it #e l'in#ice #'octane
2n&re #e l'H
(
/Bnergie a>ec l'H@/
Eien a>ec la %trochimie
;om!re"ses #co">ertes en CatalBse $ %roc#s
(. :"el?"es 1m!res
@eman#e en H
(
en constante a"gmentation <
+enI&ne $ Fromati?"es limits #ans l'essence
Transformation #es paraffines C
N-_
V amliorer )%t/K-E*
@imin"er la pro#"ction #e 2%E
CatalBse"rs a" Cl + aZo"ts #e #ope Chlore V la charge
Incorporation #',t1H)e--+iomasse*: !esoin en reformat
PROCAT 3A, jpg,2012-13
156
Bilan ;
6
en Raffinage( 12Q756777
K
PROCAT 3A, jpg,2012-13
157
Rformage de Paraffines C
352
PROCAT 3A, jpg,2012-13
158
CatalBse"r +asi?"e:
tr&s sensi!le a" / )pp!*
CatalBse"r Fci#e:
sensi!le a" / )ppm*
!somrisation des Paraffines
LgJres
PROCAT 3A, jpg,2012-13
159
L&!somrisation des Paraffines LgJres
9. %lace, Histori?"e $ RUle en Raffinerie
(. FnalBse #es Ractions
-r,bl.'es
Racti,ns $* 2r,',uv,ir, 8her',d?na'i(ue%
A. CatalBse"rs
Cinti(ue
-hases actives
3. CatalBse"r a" Tra>ail J %roc#s
7. Concl"sions $ %erspecti>es
PROCAT 3A, jpg,2012-13
160
RRle en Raffinerie
PROCAT 3A, jpg,2012-13
161
=nalyse des Ractions
n-%
-
i-%
-
)-W3-N*
HW-3 V J (4 DK/mol )Qaromati?"esR l'e-othermicit*
nW4
,?"ili!res Thermo: )traits pleins: EI:OI@, J pointills: 2F[*
PROCAT 3A, jpg,2012-13
162
=nalyse des Ractions
Tra>ailler V la pl"s !asse T possi!le
Fcti>it #" CatalBse"r sera la pl"s le>e possi!le
CatalBse"rs Fci#es o" +i-Fonctionnels L
PROCAT 3A, jpg,2012-13
163
+ifonctionnel )%t/H-.1R*: Fcti>it J /lecti>it - /ta!ilit
Polithe 0ordenite
Choi. d&un Catalyseur Bi5fonctionnel
%t/Fci#e /oli#e + Co">ert"re H
(
Fcti>it:
Pt5/l
7
O
8
-Cl NKJ. Cl" Q Pt5PrO
7
-SO
:
Q Pt5<-0OR
Pt5/l
7
O
8
-Cl: aZo"t contin" #e Cl
Ro!"stesse: 1s3 H
(
1 $ / : %t/H-.1R < Pt5/l
7
O
8
-Cl: /chage <
PROCAT 3A, jpg,2012-13
164
/
H
(
1
#canisme Bi5/onctionnel
PROCAT 3A, jpg,2012-13
165
HB#rognolBse )%t*: CracDing < ` /cission Car!ocations )Fci#e*: CracDing <
"ptimisation du Catalyseur
%ro-imit #es Fonctions Fci#es et .tal:
Crit&re #'Intimit #e 0eisI:
R
c
(
5 9.( 94
7
%
4
.@
4
.)T.1*
-9
a>ec:
- R
c
: )istan$e entre les 7 fon$tions ."
- %
4
: Pression -artielle de l@al$'ne 0Pa"
- @
4
: )iffusi1it de l@ al$'ne .
7
3s
-4
"
- T: Te.-rature &"
- 1: 1itesse de Ra$tion .ol3s
-4
3.
-8
" J T aZ"ste, 1
F/F
W1
[olithe
PROCAT 3A, jpg,2012-13
166
ParamJtre =S= Oolithe
@
4
( 94
-H
9 94
-8
T H39 3HA
%
4
94
-3
94
-3
1 7 7
(R 74 94
-N
3.7 94
-N
=ccomoder le n5C
S
-
PROCAT 3A, jpg,2012-13
167
2ran# #fi <
n-% m!-% #!-% t!-% CracDing
>oie F: V partir #e C
H
Catalyseurs & Procd
PROCAT 3A, jpg,2012-13
168
PtF;5#"R
)IP: Be4so-en!ani8er
)I<: Be4so--eMani8er
Ei?"i#e
2aI
=mlioration( =dsorption & Catalyse
F#sorption s"r Tamis .olc"laire )[olithe*
[olithe F )ETF*: ;a
9(
Q)Fl1
(
*
9(
)/i1
(
*
9(
R.(H H
(
1
,change ioni?"e:
PROCAT 3A, jpg,2012-13
169
3F: forme ;a
+
, fen]tre #'o">ert"re 3a
AF: forme K
+
, fen]tre #'o">ert"re Aa
7F: forme Ca
++
, fen]tre #'o">ert"re 3a
S-aration de n- ( iso--araffines
iso-P e,$lues"
Catalyse & =dsorption( Rsultat
PROCAT 3A, jpg,2012-13
170
- Ren#ement /"prie"r
- .oin#re >ariation 1s3 T
Raction
%roc#s #e /paration:
) .ole- )O1%*: %hase li?"i#e
) Isosi> )O1%*: %hase li?"i#e
Catalyse & =dsorption( 6 "ptions
a3 n-%MMiso-%: Isomrisation + /paration )HBsomer Eea#*
+3 iso-%MMn-%: /paration + Isomrisation )Isosi> Eea#*
PROCAT 3A, jpg,2012-13
171
<RSO0ER: )&ell F3/G, !@--0/:
ISOSI#:3/, Tamis 55
a: HBsomer Eea#
iso-%
n-%
Le /utur -@@@
@pen#ra #" .arch ,ssence ),O: *
F#sor!ant pl"s slectif: sparer
0ono-!ranchs
)i-!ranchs
PROCAT 3A, jpg,2012-13
172

F,Rrierite
3.( - 7.3 a A.7 - 3._ a
@@@Le /utur -
Racte"rs .em!ranaires J Concept L
PROCAT 3A, jpg,2012-13
173
Isomrisation C
7-H
: ;o">ea"- CatalBse"rs/%roc#s L
) Com!iner R- $ /paration
) Cape-
) @fi po"r les matria"-
) Fgencement #" %roc# L
)
/luid Catalytic CracGing
PROCAT 3A, jpg,2012-13
174
/luid Catalytic CracGing
9. Intro#"ction $ Histori?"e
%lace $ RUle en Raffinerie
1riginalit
TBpes #e Cra?"age / /lecti>it
(. FnalBse #es Ractions
Racti,ns 3 8her',d?na'i(ue)Cinti(ue
4sactivati,n
C,nditi,ns 3 1nie de la Racti,n
A. CatalBse"rs
C,'2leCit
R,le des di++rents c,sntituants
3. Concl"sions $ %erspecti>es
PROCAT 3A, jpg,2012-13
175
!ntroduction & ;istorique
/chma #e Raffinerie:
6CC B Le Grand Pro$d de Con1ersion
1ffre $ @eman#e:
S+lanchimentT #" +arril W H/C
H/C si:
C :Car!on ReZection %rocess )FCC*
H : HB#rogen F##ition %rocess )HB#rocracDing*
Car!"rants po"r le transport ),//,;C,, @iesel*
Eien a>ec la %trochimie )1lfines*
Histori?"e:
(4
i&me
/ci&cle W /i&cle #e l'F"tomo!ile
Technologie: @sacti>ation #" %roc#
PROCAT 3A, jpg,2012-13
176
Schma $ypique de Raffinerie +1,
177
PROCAT 3A, jpg,2012-13
<. ,ermeiren L 7- 'ilson
W
t
%

F
r
e
s
h

F
e
e
d
Boiling Point, C
Gas LPG Naphtha (Gasoline) LCO (Diesel) Slurry / Feedstock
Feed
3
6
0

C
2
2
1

C
C
4
C
2
/CC( Charges & Produits
Feed Properties
Density (g/ml) 0.895 - 0.935
Sulphur (wt%) 0.05 - 3.5
Nitrogen (ppm) 200 - 2000
Concarbon (wt%) 0.05 - 6.0
Nickel (ppm) 0.05 - 50
Vanadium (ppm) 0.05 - 150
Distillation (C) 300 - 800
Products
/CC( Charges 5 %tails
PROCAT 3A, jpg,2012-13
179
/CC( Produits de B 5 %tails
PROCAT 3A, jpg,2012-13
180
$;ER#"%<N=#T!E
PROCAT 3A, jpg,2012-13
181
Cra?"age: ,n#othermi?"e, n
Conditions O-ratoires* T ( P S
/CC B $hermal vs. Catalytic CracGing
0
50
100
150
n-Hexadecane at 500 C
M
o
l
e
s

P
r
o
d
u
c
t

/

1
0
0

M
o
l
e
s

C
r
a
c
k
e
d
Carbon Number
C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14
Catalytic Cracking
Thermal Cracking
Catalytic cracking avoids production of undesired C1+C2 gases
Catalyseur( %sacti:ation *
PROCAT 3A, jpg,2012-13
183
/CC Process 5 Catalyst Circulation
Products
to fractionator and gas plant
Regenerator
Riser
Stripper
Feed
Injectors
Air Blower
Flue Gas
Disengager
530C
750C
220C
Cat.
Circ.
Disengager
530
C
/CC Process B /eed !nDection
Regenerator
Riser
Stripper
Feed
Injectors
Air Blower
220
C
Cracking Reactions:
beta-scission
hydrogen transfer
isomerization
cyclization
dehydrogenation
coke formation
Feed Injection:
atomization
vaporization
Cyclone Separation:
products overhead
catalyst downwards
Cat.
Circ.
Products
to fractionator and gas plant
750
C
Disengager
530
C
/CC Process 5 Regeneration
Regenerator
Riser
Stripper
Feed
Injectors
Air Blower
220
C
Coke
burning
:
C
CO /
CO
2
H
2
O
SO
x
N
2
/ NO
x
+Heat
Cat.
Circ.
Products
to fractionator and gas plant
Heat Balance
All of the energy required
for feed vaporization and
cracking is supplied from
the heat of combustion of
coke on catalyst
The FCC unit is heat
balanced i.e. the catalyst
circulation rate is
determined by:
riser outlet T set point
feed preheat T
regenerator T
750
C
Flue Gas
Power Recovery:
turbo-expander
CO / waste heat boiler
Particulate Control:
3+4 stage cyclones
electrostatic precipitator
Emissions Control:
scrubber
FCC Process - Overview
Disengager
530
C
Regenerator
Riser
Stripper
Feed
Injectors
Air Blower
220
C
Cracking Reactions:
beta-scission
hydrogen transfer
isomerization
cyclization
dehydrogenation
coke formation
Feed Injection:
atomization
vaporization
Cyclone Separation:
products overhead
catalyst downwards
Cat.
Circ.
Products
to fractionator and gas plant
Coke
burnin
g:
C
CO /
O2
S
SOx
N
N2 /
NOx
+Heat
Coke
burnin
g:
C
CO /
O2
H
H2O
S
SOx
N
N2 /
NOx
+Heat
750
C
/CC B 'nits !ndustrielles
$ypical /CC 'nit
5000 t/d feed rate
30 m riser height
200 t catalyst inventory
20 t/min catcirc. rate
Cat. make up rate 2%
Cat/oil ratio 5-9 w/w
9orld Statistics +6772,
610kt Zeolites used in catalysts
580kt FCC catalyst used
ca. 200kt Zeolite for FCC
Rgimes d&Ecoulement en /CC
PROCAT 3A, jpg,2012-13
189
Particules de Catalyseur /CC
PROCAT 3A, jpg,2012-13
190
1 m
MATRIX Components MATRIX Components ZEOLITE-Y ZEOLITE-Y
/CC B Catalyst Composition
15%
Silica / Alumina Binder
(coating other particles)
20%
Kaolin
(filler)
35%
Zeolite-Y is Rare Earth
Exchanged to improve
hydrothermal stability
Zeolite-Y is Rare Earth
Exchanged to improve
hydrothermal stability
Metal Traps
(Ni-trap / V-trap)
15%
15%
Active Alumina
(high acidity)
Oeolites( Built fromSi"
6
E.tra5/rameUorG /rameUorG Nanoca:ity
+V 7@8 5 17 nm,
Synthesis
.
-/n
n+
Q)Fl1
(
*
-
)/i4
(
*
B
R
--
w H
(
4
#odifications
Ion ,-change CrBstal /tr"ct"res
)98H sol>e#*
Temperat"re
%ress"re
/i/Fl of
FrameworD
/i/Fl
/i
+3
)Fl
+A
+%
+7
*,
2e
+3
,
Fl
+A
+
+A
, Fe
+A
, 2a
+A
...
%olaritB
%ost-/Bnthesis F#sorption
Catalysis
H
+
, .
n+
, .eY Fcti>itB, CapacitB
/electi>itB
;anoreactor
- Fcti>itB
- /electi>itB
- /ta!ilitB
=dsorption
Emerging
2"ests $
Confinement
PROCAT 3A, jpg,2012-13
192
9 E,tension to 0O6@s% CO6@sM
Oeolites( Nombreuses Structures
PROCAT 3A, jpg,2012-13
193
Weitkamp, 2000
/CC B Oeolite < Structure
(M
n+
)
z/n
{ (SiO
2
)
y
(AlO
2
)
-
z
}
framework
M
n+
= Na
+
, H
+
, La
3+
or Ce
3+
/Ce
4+
Crystalline microporous alumino-
silicate
Macro anionic: framework (AlO
2
)
-
Charge balancing cations in channels
and cages
Number of acid sites largely depends
on the framework alumina content
Cracking reactions occur within the
microporous channels
/CC B Oeolite < Selecti:ity
Framework alumina content has a
major impact on the selectivity of
Zeolite-Y
Beta-scission is uni-molecular and
occurs at any acid site
Hydrogen transfer reactions are bi-
molecular and therefore occur to a
greater extent where multiple active
sites are available
Hydrogen transfer vs. beta-scission is
controlled using acid site density
Framework Silica Alumina Molar Ratio
24.65 (NaY)
~24.58- 24.48 (USY)
FCC Catalysts
~24.35- 24.30 (LS-USY)
Hydrocracking Catalysts
U
n
i
t

C
e
l
l

S
i
z
e

(

)
0 30 50 60 70 80 85
% Dealumination (5.0 SiO
2
/Al
2
O
3
Starting point)
Breck Correlation
24.20
24.30
24.40
24.50
24.60
24.70
0.0 10.0 20.0 30.0 40.0 50.0 60.0
196
PROCAT 3A, jpg,2012-13
Relation $aille u@c@ vs. SiF=l
Si
Si
O
Si
Si
O
O
O
O
O
O
Al
O Si
O
O
Si
Al
O
O
H
H
O
Hydothermal Treatment
Framework
Dealumination
SiO
2
Insertion
Framework Stabilization Si
Si
O
Si
Si
O
O
O
O
O
O
Al
O Si
O
O
Si
Al
O
O
H
H
O
Si
Si
Si
O
O
Si
O
O
O
Si
H
Si
O
O
O
O
H
H
H
O
O
O
O
H
H
H
H
O
Si
O
O
O
O
Si
O
O O
+ 4 H
2
O
H
2
O
H
2
O
+ 2 AlO
2
O
O
O
O
H
H
H
H
O
O
O
O
H
H
H
H
%salumination
$raitement ;ydrothermal
197
PROCAT 3A, jpg,2012-13
%salumination( #soporosit
PROCAT 3A, jpg,2012-13
198
I/1TH,R.,/
P: TBpe I
/teame#-P: TBpe IC
%1R1/IT,
P: .icropores
/teame# P: .icro- $ .eso-pores
Step 2: carbenium ion takes a proton from naphthene
molecule; itself being converted to a paraffin
CH
2
CH
CH
3
CH
3
+
CH
2
CH
CH
2
CH
2
CH
2
CH
2
H
CH
2
CH
CH
3
CH
3
+
CH
2
CH
CH
2
CH
2
CH
2
CH
2
H
[AlO
2
]H
Zeolite Site
CH
CH
CH
3
CH
3
CH
CH
H
CH
3
CH
3
+
Step 1: olefin is protonated to form
a carbenium ion at acid site
Summar:
Olefin ! "aphthene #araffin ! Cclo$olefin
Cclo$olefins can %o on donatin% hdro%en to
further olefins& e'entuall formin% aromatics
$H
2

naphthene
cclo$paraffin
cclo$olefin cclo$diolefin aromatic
$H
2

$H
2

A 1lefin + ;aphthene A %araffin + Fromatic


Step 3: cclic carbeniumion returns a proton to
the acid site; itself being converted to a cyclo-olefin
CH
CH
CH
2
CH
2
CH
2
CH
2
CH
+
CH CH
2
CH
2
CH
2
CH
2
H
[AlO
2
]H
Zeolite Site
[AlO
2
]
-
Zeolite Site
/CC Chemistry B ;ydrogen $ransfer
199
PROCAT 3A, jpg,2012-13
9;< -
PROCAT 3A, jpg,2012-13
200
/econ#arB R- of %rime Importance: HB#rogen Transfer )b H
-
*
A 1lefin + ;aphtene A %araffin + Fromatic
% $ F less prone to (
n#
CracDing 2asoline /electi>itB
.ilesone in the CatalBsis In#"strB
Peoliti$ 6CC Catalyst
Tuna+le /$ti1e site )ensity*
HI2H E10
EC"N"#!C RES'L$
PROCAT 3A, jpg,2012-13
201
98N3: Intro#"ction of a @isr"pti>e TechnologB
37 Bears of Contin"o"s Incremental Impro>ements
HB#rogen transfer reactions con>ert Smore reacti>eT
olefins to Sless reacti>eT paraffins
2asoline less olefinic / more paraffinic res"lting in
&ig&er gasoline selec!i$i!*
re+#c!ion in oc!ane n#m?er
lo;er K' selec!i$i!*
E%2 is less olefinic res"lting in lower C
3
W
's in the C
3
stream
lo;er 5l1* fee+ "#ali!*
lo;er ET9E fee+ "#ali!*
/CC B !mpact of ;
6
$ransfer
/CC B !mpact of ;
6
$ransfer
PROCAT 3A, jpg,2012-13
203
+ .o#"la!le par QFlR
/CC B Controlling Selecti:ity
Feed / Bottoms
(Heavy Fuel Oil)
LCO
(Diesel)
Naphtha
(Gasoline)
LPG
(C
3
s+C
4
s)
Fuel Gas
(C
1
+C
2
)
Thermal
Cracking
Matrix
Cracking
Zeolite
Cracking
Low
Rare Earth
Perhaps over simplifying, but
Thermal cracking is largely responsible for fuel gas formation
Matrix cracking is largely responsible for conversion of heavy
feed / bottoms molecules to diesel range molecules
Zeolite is largely responsible for cracking diesel range
molecules into the gasoline range
High rare earth on zeolite increases hydrogen transfer thereby
preserving gasoline, low rare earths favour LPG selectivity
Na
2
O on Sieve (wt.%) 13% 3-4% 3-4% <1% <1%
Al
Si
NaOH NaY
NaNH
4
Y
NaRENH
4
Y
USY
CREY
RE-USY
USY
CREY
RE-USY
USY
CREY
RE-USY
exch.
H
2
O
calc. exch. calc.
Prparation de Catalyseurs /CC
Octane-Enhancing Zeolitic FCC Catalysts,J. Scherzer, 1990, p.73
205
PROCAT 3A, jpg,2012-13
I Commercial $ypes of /CC Preparation
In Situ
Zeolite produced by insitu
zeolitization of Spray
Dried/ Calcined Clay
Matrix generated during
insitu process
Filter/Wash
Dry
Calcine
Product
Silica Binder
Zeolite & Matrix
Prepared Separately
Mix binder,clay, matrix
materials, zeolite
Spray Dry
Wash / Exchange
Dry
Product
ACH Binder
Zeolite & Matrix
Prepared Separately
Mix Low Soda
binder,clay, matrix
materials, zeolite
Spray Dry
Calcine
Product
Pept. A
l2
O
3
Binder
Zeolite & Matrix
Prepared Separately
Binder/matrix consists
of high levels of
peptized alumina
Spray Dry
Calcine
Wash / exchange*
Dry*
Product
*May not be needed 206
PROCAT 3A, jpg,2012-13
Spray %ryer Principles
9h. Spra. )r. :
HighlB s"ite# for contino"s pro#"ction of pow#ers from
p"mpa!le s"spensions
Forms spherical particles
) 2r,vides +,r +luid)liAe +l,> 2r,2erties
Control o>er pro#"ct ?"alitB stan#ar#s
) 2article siRe distributi,n
) residual ',isture c,ntent
) bulA densit?
%ro#"ces the most homogeneo"s pro#"ct for
m"lticomponent sBstem
) 2articles have sa'e che'ical c,'2,siti,n as +eed
207
PROCAT 3A, jpg,2012-13
Spray %ryer Principles
;.pical )r.er Schematic
/praB @rBing /teps
At,'iRati,n
MiCin# ,+ dr,2lets and
h,t #ases
-article dr?in#
-r,duct rec,ver?
Spray Dryer
Cyclones
System Vent Fan
Recycle Fan
Feed Pumps
Atomizers
Fuel Source
Combustion
Air Blower
Air
Heater
Ambient
Air
Ambient
Air
Auxiliary Heat
Source
NO
2
Converter
Bayliss Technologies, Inc. SprayDrying Brochure
Spray %ryer Principles
Press"re or Sin&le $l"i( <o11le
Narr,> 2article siRe
distributi,n
C,'2licated +eed 2u'2
) Di#h 2ressure re(uired
Si'2le device
Susce2tible t, 2lu##in#
Re(uires abrasi,n resistant
'aterials ,+ c,nstructi,n
Ca2acit? li'ited t, < 1-M 2er
n,RRle
Can use 'ulti2le at,'iRin#
devices in 4r?er
Niro, Inc Sales Brochure
Bayliss Technologies, Inc. SprayDrying Brochure
.i-e# Flow @rBing
ress#re No88le in 3pspra*
%ress"re ;oIIle
%o-%#rren! Br*ing
Centrif"gal )0heel* FtomiIer
%o-%#rren! Br*ing
Air Flow
Air Flow
Spray %ryer Principles
)r.in& Cham=er )imensions & Con>i&"rations
Co-current
Countercurrent
Niro, Inc Sales Brochure
Bayliss Technologies, Inc. SprayDrying Brochure
Air Flow
210
PROCAT 3A, jpg,2012-13
0
1
2
3
4
5
6
7
8
0 20 40 60 80 100 120 140 160 180 200
#ean Particle Si0eL microns
%
r
y
i
n
g

C
h
a
m
b
e
r

%
i
a
m
e
t
e
r
L

m
e
t
e
r
s
#ean Particle %iameter :s@ #inimum Chamber %iameter
for Rotary +9heel, =tomi0ers
Mean Particle Size Range
FCC Catalyst
Spray %ryer Principles
Niro, Inc Sales Brochure
211
PROCAT 3A, jpg,2012-13
/CC( /le.ibilit accrue par =dditifs
FCC W ( Racte"rs co"pls
Reacte"r: TG774YC, Ftmosph&re R#"ctrice
Rgnrate"r: TGH74YC, Ftmosph&re 1-B#ante
TBpes #'a##itifs
%romote"rs #e Com!"stion
%ro#"ction #'1lfines - 1ctane +ooster
%assi>er le ;i $ C
Transfert #e /1
^
@e;1-
%romote"r #e Fl"i#isation
+ottoms CracDing F##iti>e

PROCAT 3A, jpg,2012-13
212
Air Blower
FEED
FLUE GAS
PRODUCTS
dilute phase
dense
phase
(bed)
Carbon burning (regen. bed)
C (coke) + O
2
(g) = CO (g)
C (coke) + O
2
(g) = CO
2
(g)
/CC B Regenerator Combustion =ids
Pt base CO promoters are
commonly used to ensure
complete combustion of
coke to CO
2
in the regen.
bed (dense phase)
Recently non-Pt based CO
promoters have become
available
Excessive CO can react with O
2
in the dilute phase
CO + O
2
(g) = CO
2
(g) + heat
The heat released can cause
afterburning i.e. excessive
temperatures of cyclones and
flue gas line
Production d&"lfines( OS#54
PROCAT 3A, jpg,2012-13
214
Feed / Bottoms
(Heavy Fuel Oil)
LCO
(Diesel)
Naphtha
(Gasoline)
LPG
(C
3
s+C
4
s)
Fuel Gas
(C
1
+C
2
)
Thermal
Cracking
Matrix
Cracking
Zeolite
Cracking
Low
Rare Earth
2 3 4 5 6 7 8 9
1lefins Car!on ;"m!er
1
l
e
f
i
n

P
i
e
l
#

)
w
t
6
*
+ase + [/.-7
OS#54( %istribution des "lfines
+ase FCC CatalBst
P)0-5 crac1s %
2
O
gasoline range
&*+rocar?ons !o prop*lene an+ ?#!*lenes
Eien a>ec la %trochimie: /TRFT,2I:O, <
PROCAT 3A, jpg,2012-13
215
/CC B En:ironmental =dditi:es
The FCC fee# contains / $ ; contaminants
S,'e ,+ the S 3 N ends u2 in the c,Ae ,n catal?st
that is burned),++ in the re#enerat,r
S in c,Ae +,r's S@
<
and S@
6
c,llectivel? An,>n as
S@
C
N in c,Ae is ',stl? c,nverted t, N
<
, h,>ever l,>
levels ,+ a c,'2leC 'iCture ,+ ,Cides $'ainl? N@%
c,llectivel? An,>n as N@C are als, +,r'ed
Fee#
/+;
/1
-
;1
-
Air Blower
FEED
( Sulphur )
FLUE GAS
PRODUCTS
( SOx )
( H
2
S )
REGENERATOR
Typical Feed S to Coke
HTVGO < 5 wt%
VGO 5-10 wt%
Residue > 10 wt%
SOx formation:
S (coke) + O
2
(g) = SO
2
(g)
SO
2
(g) + O
2
(g) = SO
3
(g)
/CC B S"
.
/ormation
/CC B S". Reduction =dditi:es
Capt"re phase: h?dr,talcite ,r s2inel t, ca2ture S@
6
in the re#enerat,r
1-i#ants: Ce B " t, re2lenish ca2tured S@
6
via ,Cidati,n ,+ S@
<
Release agent: " used t, assist re#enerati,n ,+ additive in the react,r
Mg
6
Al
2
(OH)
18
Hydrotalcite
Mg Al
2
O
4
Spinel
Mg, Al
OH
OH
Mg, Al
OH
OH
Mg, Al
OH
OH
Mg, Al
OH
OH
Air Blower
FLUE GAS
PRODUCTS
FEED
( Sulphur )
( decreased SOx )
( increased H
2
S )
/CC B S"
.
Reduction 'sing =dditi:es
formation of metal sulphate
SO
3
(g) + MeO(s) = MeSO
4
(s)
Riser: reduction of metal sulphate
MeSO
4
(s) + 8 [H] = MeS (s) + 4 H
2
O (g)
Riser/Stripper: hydrolysis of sulphide
MeS (s) + H
2
O (g) = MeO (s) + H
2
S (g)
Regenerator: SO
2
oxidation
SO
2
(g) + O
2
(g) = SO
3
(g)
/CC( Tuelques ChiffresC
RefinerB process that ScracDsT high molec"lar weight
hB#rocar!ons to lower molec"lar weight
93 .illion +arrels per #aB )(.(7 !illion liters/#aB*
RefinerB process that pro>i#es G74 6 of all transportation
f"els in#irectlB
%ro>i#es GA7 6 of total gasoline pool #irectlB from FCC
pro#"ce# naphtha
%ro>i#es A4 6 of #iesel an# 944 6 heating f"el
PROCAT 3A, jpg,2012-13
220
C/CC( Tuelques Chiffres
G N4 micron poro"s silica-al"mina !ase# spheres
4.H gr/cc S!"lDT #ensitB, (.4 gr/cc SsDeletalT #ensitB
9(4- A(7 gr of cat Scons"me#T /!arrel W 9NA liters
F!o"t _44,444 tons catalBst/Bear worl# wi#e, for a!o"t A44
refiners.
Cons"mption #epen#s on fee#stocD ?"alitB, mainlB
irre>ersi!le poisoning !B >ana#i"m
PROCAT 3A, jpg,2012-13
221
;ydrocraquage
PROCAT 3A, jpg,2012-13
222
Procds )nrateurs de %istillats
#oyens
PROCAT 3A, jpg,2012-13
223
)=S"!LS( a, S & =romatiques
b, !ndice de Cetane :s@ WSX
PROCAT 3A, jpg,2012-13
224
;ydrocraquage( Coupes
+YC & RendementsL Zmasse,
PROCAT 3A, jpg,2012-13
225
"ptions de Procds d&;CA
PROCAT 3A, jpg,2012-13
226
Two /tage
/eries Flow /ingle /tage
Racteurs $ri5Phasiques
PROCAT 3A, jpg,2012-13
227
Con:ersion des Rsiduus +447
K
YC,
Proc(s
PROCAT 3A, jpg,2012-13
228
C"NCL'S!"NS
PROCAT 3A, jpg,2012-13
229
Raffinerie Simple +%but &S7,
PROCAT 3A, jpg,2012-13
230
Raffinerie Con:ertissante +fin &Q7,
PROCAT 3A, jpg,2012-13
231
Raffinage du /utur+6717 B 6767,
PROCAT 3A, jpg,2012-13
232