Beruflich Dokumente
Kultur Dokumente
November 2004
Pedro da Silva
Why Hydroprocessing?
BEFORE
NOW
Why Hydroprocessing?
Why Hydroprocessing?
Market of solid catalysts in refining, (IFP data,1994)
Catalytic cracking
Hydroprocessing
Claus
Hydrocracking
Reforming
isomerization
other
TOTAL
tons /year
440 000
80 000
20 000
8 000
5 000
1 000
12 000
566 000
propane
butane
HDT
Reforming
gasoline
H2
kerosene
Hydrodesulphurisation
diesel
Vacuum Distillation
Crude
Atmospheric Distillation
naphtha
Catalytic
Cracker
FCC
Visbreaking
Heavy fuel
propane
butane
HDT
Reforming
gasoline
H2
kerosene
Hydrodesulphurisation
diesel
Vacuum Distillation
Crude
Atmospheric Distillation
naphtha
HDS
Catalytic
Cracker
FCC
Visbreaking
Heavy fuel
propane
butane
naphtha
Atmospheric Distillation
Reforming
gasoline
H2
kerosene
Hydrodesulphurisation
diesel
HDS
Vacuum Distillation
Crude
HDT
Catalytic
Cracker
FCC
Visbreaking
Heavy fuel
Pressure
(bar)
Temperature
(C)
Flowrate/
catalyst volume
(h-1)
Naptha
Kerosene
Diesel oil
VGO
ARDS
VGO, residue
hydrocracker
7-30
15-50
15-90
30-100
80-200
280-320
300-330
320-390
340-410
370-410
3-10
2-6
1-4
1-2
0.2-0.5
100-200
370-410
0.5-1.5
- The most important parameters followed in these units (apart from product
qualities!) are the temperature and unit pressure drop
- The difference on activity and stability of different catalysts is measured by C
Chemical Reactions in
Hydroprocessing
Hydrogen consumption
Refractory compound
Chemical Reactions in
Hydroprocessing
A21 41838-01_1.DATA
C1
C3
BT:Benzothiophne
C2
DBT:Dibenzothiophne
S
C2
C4
S
C3
S
S
C4+
48 000 V
46 000
44 000
42 000
40 000
38 000
36 000
34 000
32 000
30 000
28 000
26 000
24 000
22 000
20 000
18 000
16 000
14 000
12 000
10 000
8 000
6 000
4 000
2 000
0
-2 000
-4 000
-6 000
0
1
C1
SPW 0.20
C5
10
11
Soufre
rfractaire
12
13
14
16
17
18
19
20
RT [min]
21
22
Chemical Reactions in
Hydroprocessing
4,6-DiMeDBT
2,4,6-TriMeDBT
S
1,4,6-TriMeDBT
4,6-EtMeDBT
4,6-DiEtDBT
3,4,6-TriMeDBT
4,6-PrMeDBT
Chemical Reactions in
Hydroprocessing
Chemical Reactions in
Hydroprocessing
Chemical Reactions in
Hydroprocessing
Rgime thermodynamique
(HDA)
Equilibre thermodynamique
% HDA
HDA
Rgime cintique
(HDA)
HDS
T1
T2
Temprature (C)
Chemical Reactions in
Hydroprocessing
- Hydroprocessing reactions are exothermic
- Temperature and pressure are needed for hydroprocessing reactions
- Reactor delta temperature:
8-9C rise per 1 wt% sulphur removal
1-2C rise per 1vol% of polyaromatics removal
1C rise per bromine number removal
Opration normale
four
0
R1
lit 1
quench
lit 2
R1
temprature
Simplified Scheme of an
Hydrodesulphurisation Unit
Make-up
hydrogen
Make-up
compressor
to fuel
gas
Heat
Exchangers
Partial by-pass
Raw feed
Furnace
2
Quench
Reactor
Recycle
compressor
H.P.
Flash drum
Air
coolers
Stripper
Catalyst bed
Varies between 3 to 15 m
Catalyst support
grid
Mixing chamber
Quench
distributor
Vapor/liquid
distribution tray
Unloading nozzle
Outlet collector
Catalyst bed
reactor outlet
collector
Additional
gasketing
15
10
0
0
100
200
300
400
Days on stream
500
600
Hydroprocessing Catalysts
- Generally HDS catalysts are constituted by metal oxides from columns
VIA (Mo,W) and VIIIA ((Co),Ni) periodic table
- The active phase of HDS catalysts consists in the sulphided form of these
oxides MoS2 slabs
..
.
.
.. .
Co
..
.
.
30
Mo
S
Mo
Al2O3
- Co or Ni are activity promoters and decorate the edge of MoS2 slabs
- CoMo catalysts are generally used for low pressure units and were the main
objective are HDS reactions
- NiMo catalysts are generally used for higher pressure units and were the
main objective is density and cetane gain (hydrogenation reactions)
Hydroprocessing Catalysts
Used catalyst
Sulphide + coke
Lets do it again
Rotary Kiln
Oven
Spent Catalyst
Hot Air
Catalyst Loading
Catalyst loading
Local porosity,
Catalyst loading
Catalyst loading
Catalyst Activation
in situ
Sulphidation
Oxide catalyst
MoO3
reactor
H2S
DMDS
H2 Activation
Active catalyst
MoS2
reactor
preSulphided preSulphiding
Sulficat, Acticat,
MoOxSy
EasyActive
ex situ
Final step
Oxide catalyst
MoO3
ex situ
Under H2
T > 230-250C
Reduction
to MoO2
Unactive phase
ex situ
Catalyst Activation
Reactor inlet temperature (C)
350
300
Catalyst sulphiding
(320-350C)
250
Catalyst wetting
200 (liquid flow)
DMDS injection
150
100
50
0
Drying
(120-150C)
Unit under pressure
8
10
12
Time (hours)
14
16
18
20
Kinetic Models
d [S ]
= k [S ]
dt
Feed + H2
Sout
Sin
tc
Sin d [S ]
tc
d [S ]
= k dt
= k dt
0
0
Sout [S ]
[S ]
Eact
RT
k0 e
Sin
ln
= k tc =
LHSV
Sout
Eact
T =
ln(Sin / Sout ) LHSV
R ln
k0
Desulphurized product
+ H2 + H2
Kinetic Models
Typically, for HDS reactions on diesel and VGO
Eact = 25000 - 29000 cal/mole
Example - Catalyst volume = 200 m3
Catalyst A
Flowrate = 300 m3/h
Bed 1 Tin = 345C, Tout = 365C, Bed 2 Tin = 360C, T = 370C
WABT = 362,5C
Sin = 7000 wtppm
Sout = 40 wtppm
k0 = 1,5E10 h-1
Catalyst B
Flowrate = 280 m3/h
Bed 1 Tin = 342C, Tout = 362C, Bed 2 Tin = 352C, T = 362C
Sin = 7000 wtppm
Sout = 33 wtppm
WABT = 359,9C
k0 = 1,4E10 h-1
Temperature
Max temp
Cycle length
SOR
EOR
Time
Max temp
Max temp
Temperature
Cycle length
Time
Cycle length
Time
400
390
Catalyst A
380
370
10C difference
Catalyst B
360
350
340
330
320
0
40
80
120
160
200
240
Days on stream
280
320
360
400
390
380
370
360
350
Normalized temperature
1,5C/month
340
Actual temperature
3,5C/month
330
320
0
40
80
120
160
200
240
Days on stream
280
320
360
Hydroprocessing Unit
Cold Scheme
Advantages: higher H2% in recycle gas, simpler, light feeds can be processed
Disadvantages: lower energy efficiency, larger high pressure separator
Hydroprocessing Unit
Hot Scheme
Advantages: better energy efficiency, no need for stripper feed heating (most cases)
Disadvantages: need for recycle gas amine wash, loss of hydrogen
Hydroprocessing Unit
Stripping section
The objective of the stripping section is to removed light ends from the diesel (H2S, CHs)
and/or to remove products lighter than the unit main product
Hydroprocessing Units
Gasoline hydrotreaters
In general, the objective of the gasoline hydrotreaters is to remove sulphur and nitrogen
from reformer or isomerization feeds.Indeed, sulphur and nitrogen will poison and
degrade the performances of reforming and of isomerization catalysts
Gasoline hydrotreaters operate on 100% gaz phase, there is no need for distribution trays
Hydroprocessing Units
Kinetic Models
d [S ]
n
= k [S ] , n > 1
dt
Feed + H2
Sout
Sin
tc
Sin d [S ]
tc
d [S ]
= k dt
= k dt
n
n
Sout
0
[S ]
[S ] 0
Eact
RT
1
k0 e
1
1
n 1 n 1 = k tc =
LHSV
n 1 S out S in
T =
Eact
1
1
n 1 n 1 LHSV / k 0
R ln
n 1 S out S in
Desulphurized product
+ H2 + H2