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72
PROCAT 3A, jpg,2012-13
#oteur ;CC!( /onctionnement
PROCAT 3A, jpg,2012-13
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
PROCAT 3A, jpg,2012-13
To!al
=dquation $echnologie #oteur 5
Lubrifiants 5 Carburants
75
PROCAT 3A, jpg,2012-13
To!al
alorisation de la Biomasse
,fficacit ,nergti?"e
,ffet C1
(
, empreinte H
(
1L
0ell-to-0heel FnalBsis <
76
PROCAT 3A, jpg,2012-13
Bio5Energies( $he Big picture C
Ressources
Cultures ddies annuelles et
pluri-annuelles
plantes et herbacs
sylviculture
Co-produits des cultures ddies
pailles et tiges de crales et
olagineux
rsidus forestiers
Autres co-produits et rsidus
industriels
mnagers
autres
Collecte
Transport
Stockage
Pr-
traitement
Technologies de conversion
Voie thermochimique
combustion
pyrolyse
thermolyse
gazification
Valorisation du gaz de synthse:
purification,sparation
procds catalytiques (FT,
MeOH
Voie biologique
ractions enzymatiques
fermentation
distillation, purification
Dbouchs
Energie
chaleur, vapeur
lectricit
Carburants
naphta
essence
jet
distillats
mthanol
thanol
DME
EMHV; EEHV
ETBE
hydrogne
Produits
glycrol
spcialits FT
alcools
autres
Voie olochimique
raffinage chimique et physique
esterification
hydrotraitement
sparation, purification
77
PROCAT 3A, jpg,2012-13
La Raffinerie du /utur -
78
PROCAT 3A, jpg,2012-13
To!al
Popularit vs. SuccJs !/P School
79
PROCAT 3A, jpg,2012-13
%fis Energtiques +R#,( 6747
K
J#!#ris, 2005
80
PROCAT 3A, jpg,2012-13
/acteurs de Con:ersion
PROCAT 3A, jpg,2012-13
81
9 )!a!is!ical :e$ie;
Le S & les ;ydrotraitements
PROCAT 3A, jpg,2012-13
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*
PROCAT 3A, jpg,2012-13
83
Coupes PtroliJres( S & Co@
PROCAT 3A, jpg,2012-13
84
BR'$S( Prsence de SL N
PROCAT 3A, jpg,2012-13
85
MStraight5RunN vs. Processed /ractions
PROCAT 3A, jpg,2012-13
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
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