Académique Documents
Professionnel Documents
Culture Documents
for
Gas
G to Li
Liquids
id (GTL)
XTL Fundamentals
1-3 December 2009
2009, Cape town
Turn-over
Turn
over of $ 8 Billion
23,000 employees worldwide in 21 locations
HQ in Paris, other main operating centres for onshore business
include Rome, Houston, Claremont, The Netherlands, Kuala-Lumpur,
Abu-Dhabi, Delhi
Built the first commercial GTL p
plant at Oryx,
y , Qatar,
Q
, which started up
p
in 2007 and operating successfully
Built the Statoil pilot plant at PetroSA
PRESENTATION OVERVIEW
Introduction
Specifics of Syngas for GTL / XTL
Syngas Generation Routes and Technologies
Challenges and Options in optimizing Syngas
generation
Brief Scouting Comparison
Innovative Developments
Conclusions
PRESENTATION OVERVIEW
Introduction
Syngas specifics for GTL
Syngas Routes and Technologies
Challenges and Options in optimizing Syngas
generation
Brief Scouting Comparison
Innovative Developments
Conclusions
INTRODUCTION
Typical
World Scale
Plant Capacity
Equivalent
Natural Gas
(MMSCFD))
30 years NG
requirement
((TCF))
Large H2 Plant
100 mmscfd
45
0.5
Ammonia
2000 mtpd
55
0.6
Methanol
p
3000 5000 mtpd
100 -160
1.1 - 1.8
GTL
30 150 K bpd
300 1400
3.0 14.0
LNG
5 - 8 mm tpy
800 -1200
8.5 - 13.0
Coal
Nat.
Gas
Methanol
Captive
p
p
power
DME
Fuel Cells
MTBE
MTO
Syngas
GTL
Bio-mass
Bio
mass
N hth
Naphtha
Diesel / Gasoil
Lubes
Waxes /
Specialties
Natural Gas
+
Oxygen
Syngas
Generation
Fischer-Tropsch
Synthesis
Hydrogen
Steam
Excess
Power
Carbon
Monoxide
+
F-T Products
Upgrading
Power
Plant
Waxy
Intermediates
Steam
Water
Jet Fuel,, Diesel,,
Naphtha
XTL Fundamentals, 1-3 Dec, 2009, Cape town
PRESENTATION OVERVIEW
Introduction
Syngas specifics for GTL
Syngas Routes and Technologies
Challenges and Options in optimizing Syngas
generation
Brief Scouting Comparison
Innovative Developments
Conclusions
For F-T, the required ratio is ~ 2.0 with minimized level of CO2
and inerts
10
11
2n H2 + n CO
n (-CH2-) + n H2O
n CO + n H2O
n H2 + 2n CO
=
=
n H2 + n CO2
(WG Shift)
n ((-CH
CH2-)) + n CO2
H2/CO ~2.0
C7H16 requires
q
H2/CO of 2.10
C20H42 requires H2/CO of 2.05
M th
Methanol
l
5H2 + CO + CO2
2CH3OH + H2O
12
e cata
yst
Fe
catalyst
CO catalyst
Operating conditions
13
Steam
Air
O2
Tail gas
F-T Synthesis
& Separation
Generation
H2
Proc. Cond
Power
Fl gas
Flue
Water
Steam
System
Air
Separation
Steam-Power
system
Reac. water
PSA
~ 70
Products
Work-Up
H2
Synfuels
H2 plant
~ 230
14
Air Separation
Unit
Natural
Gas
Oxygen
(99.5% vol)
CO-Shift
and
PSA Units
Steam
Reforming
H2/CO = 3.36
Hydrogen
(99.9% vol)
Natural Gas
Raw Gas
Partial
Scrubbing and
Oxidation Steam Generation
H2/CO = 2.30
C5+
Extraction
Products
Separation
Light Ends
to Fuel
C5+ cut
Hydrocracking
Unit
H2/CO = 1.76
Fischer-Tropsch
Fi
h T
h
Reactor
Middle
Distillate
H2/CO = 2.10
15
PRESENTATION OVERVIEW
Introduction
16
Steam route
g (SMR)
(
)
Steam-methane reforming
Catalytic, endothermic process ( upto 950 C)
CH4 + H2O = 3 H2 + CO (NG feed ; 206 kJ/mole)
H d
Hydrogen
Contributor
C t ib t ; CO deficient
d fi i t for
f F-T
FT
[ C6H12 + 6H2O = 12 H2 + 6 CO for Naphtha feed ]
Oxygen route
17
Auto-thermal
Auto
thermal reforming (ATR)
CH3.74 + 0
0.6
6 H2O + 0.57
0 57 O2 + 0.08
0 08 CO2 = 1.82
1 82 H2 + 0.91
0 91 CO + 0.17
0 17 CO2 + 0.65
0 65 H2O
18
Increases
ratio
ti
Application
Domain
NG-SMR
NG-SMR
NG-SMR
NG-ATR (partial)
NG-SMR
X
X
NG-POx
CTL
NG: SMR + POx
19
POx
ATR
COMB
SMR with
ith CO2 addition
dditi
3CH4 + 3H2O
= 3CO + 9H2
CO2 + H2
= CO + H2O
3CH4+2H2O +CO2 = 4CO + 8H2
SMR
with process CO2 recycle
1
H2 / CO ratio
XTL Fundamentals, 1-3 Dec, 2009, Cape town
20
Steam Reforming
(SMR)
Conventional SMR
Compact reforming
Regenerative reforming*
Non catalytic
Catalytic
Combination Routes
Combi reforming
SMR + ATR in
i split
li -parallel
ll l
2-step reforming
SMR + ATR (
(OBS)) in series
GHR* + ATR/OBS in series
Combi Pox
POx + SMR in parallel
POx / ATR + EHTR* in parallel
21
Steam Reforming
(SMR)
Conventional SMR
Compact reforming
Regenerative reforming*
Non catalytic
Catalytic
Combination Routes
Combi reforming
SMR + ATR in
i split
li -parallel
ll l
2-step reforming
SMR + ATR (
(OBS)) in series
GHR* + ATR/OBS in series
Combi Pox
POx + SMR in parallel
POx / ATR + EHTR* in parallel
22
15
Fuel
180
Steam
Steam
Reforming duty
100
150 C
1100 C
Steam
880 C
Air
300 C Syngas
30
45
Feed
10
XTL Fundamentals, 1-3 Dec, 2009, Cape town
23
Burners
Catalyst tubes
Outlet system
Flue Gas
T
Tunnels
l
Transfer Line
Reformed
gas
24
Temp
perature Deg C
Fuel / air
gas/
steam
800
600
200
0.2
0.4
0.6
Fraction down tube
0.8
catalyst
a e
flame
tube
STEAM REFORMING
PROs
Simple,
Simple highly proven
Reliable and flexible
No need for Oxygen
Cost-effective (esp. for H2/CO >3 on NG)
CONs
26
Steam Reforming
(SMR)
Conventional SMR
Compact reforming
Regenerative reforming*
Non catalytic
Catalytic
Combination Routes
Combi reforming
SMR + ATR in
i split
li -parallel
ll l
2-step reforming
SMR + ATR (
(OBS)) in series
GHR* + ATR/OBS in series
Combi Pox
POx + SMR in parallel
POx / ATR + EHTR* in parallel
27
Non-equilibrium based
E ilib i
Equilibrium
based
b d
28
O2
feed gas
Gasifier
steam
Non catalytic
Non-catalytic
Gasifier at 1200-1400C
Feed gas preheated with little
or no steam addition
Large oxidant consumption
H2/CO ratio typically 1.6
1 6-1
1.8
8 on
NG and 0.4 - 0.6 on Coal
Low CO2, very low CH4 slip in
syngas
Pressures can be upto 70 bar
syngas
29
PARTIAL OXIDATION
POx
Reactor
WH Boiler
S/C Overall
O2/C
: 0.2
: 0.64
NG feed
1350C, 60 bar
O2 + Steam
Steam
H2/CO
: 1.9
Syngas
30
PARTIAL OXIDATION
PROs
Low CO2/CO ratios due to very less steam and high temperature
Not limited by catalyst temperature limits (higher temp --> higher
CO/H2)
C handle
Can
h dl variety
i
off heavier
h
i feeds
f d
Allows higher
g
pressure
p
syngas
y g (upto
( p 60 bar))
CONs
oxygen
feed g
gas
fuel gas
CPO
steam
syngas
PROs
CONs
33
Conventional SMR
Compact Reforming
Pre-reforming
Non catalytic
Catalytic
Hybrid processes
Combined Reforming
Gas Heated Reforming (GHR)*
EHTR Post Reforming
POX+EHTR
34
AUTOTHERMAL REFORMING
O2/C
S/C overall
CO2/C
O2 from ASU
Steam
NG Feed
: 0.64
0 64
: 0.8
: 0.3
1050C , 35 bar
Sulphur
Removal
H2/CO
: 2.0
Steam
35
AUTO--THERMAL REFORMER
AUTO
oxygen
1.15 te/te natural gas
~1.15
f d gas from
feed
f
fired
fi d heater
h t
~700C
steam
~2
2 te/te natural gas
syngas
1020C
36
1.7
1.2
0.6
Residual methane
0.30
0.48
1.05
93
9.3
77
7.7
55
5.5
H2/CO
2.65
2.31
2.08
Severity
Low
Medium
High
37
AUTOTHERMAL REFORMING
PROs
CONs
38
39
AIR--BASED ATR
AIR
PROs
No commerciall application
was realized
l
l d
No ASU
N
More suited for FPSO
Potentially
ote t a y lower
o e cost for
o ssmaller
a e p
plants
a ts
Apparently simpler process
CONs
40
Developed by ExxonMobil
PROs
CONs
41
%C0YIELD
SMR
70
85
92
96
100
ATR
POX
COPOX
IDEAL
24
2.4
1.8
1.9
2.1
42
Conventional SMR
Compact Reforming
Pre-reforming
Non catalytic
Catalytic
Hybrid processes
Combined Reforming
Gas Heated Reforming (GHR)*
EHTR Post Reforming
POX+EHTR
43
HYBRID PROCESSES
Combi reforming :
2-step reforming :
Combi POx
COMBI REFORMING
45
COMBI REFORMING
PROs
CON
CONs
46
LURGI'S COMBI
COMBI--REFORMING
47
Advantages :
Technology Status
Proven
~ 400 MMSCFD Syngas ( ~17,000 bpd ) with single OBSR unit
48
Steam drum
Flue
Fl gas
Process
Steam
Excess
Steam
Feedstock
to and from
heat recovery
Hydrogen
Recycle
Oxygen + steam
By-pass
Feed
Combustion air
Fuel gas
Hydrodesulphurizer
ZnO bed
to Heat Recovery
49
Auto-Thermal
Auto
Thermal Reforming
(ATR)
Regenerative reforming +
O2-based
Regime : Provider
Combi
Compact
Severe
: Lurgi* / Petro SA
: BP-Davy* / One Synergy
: Rentech
Non-Catalytic
Shell
Catalytic
Fixed bed
Air Blown
Fluidised
Combi
:
:
:
:
: Conoco (CoPOx)*
Topsoe*-Sasol-Chevron
Syntroleum*
Syntroleum
ExxonMobil *
Lurgi * / GTL F-1
50
Regenerative reforming
Use
high-level
U off process gas hi
hl
l heat
h t for
f partt reforming
f
i
Substantial reduction in reformer duty and firing
Configurations
z
2 iin -1
1 outt
Enhanced
2 in - 2 out
Advanced
51
Enhanced Heat
Transfer Reformer
2 iin - 1 outt
52
53
SMR--EHTR INTEGRATION
SMR
Process
Steam
Desulphurization
HC feed
Primary
reformer
Reformed gas
For heat recovery
54
POX + EHTR
2
Natural Gas
/(CO2)
and Steam
Oxygen
NG
Syngas
y g
Advanced
Gasifier
EHTR
Hot Syngas
toEHTR
55
Start-up Steam
SMR
H2
Synthesis Gas
1,845 Gcal/hr
6,700 Gcal/hr
Natural
Gas Feed
Shell MDS
Kerosene
EHTR
Synthesis
Gas
4,018 Gcal/hr
Naphtha
HPC
HPS
(Heavy Paraffin
Synthesis)
+
Distillation Facilities
SGP
11 Gasifiers
G
Gasoil
il
Paraffin
CO2 Compressor
O2
28 MW
2 x 4,500 tpd Air
Separation Unit
CO2
Offgas
Fuel
Wax
Offgas
Fuel
Water
CO2 Removal
Water
56
PROs
CONs
57
syngas
58
ROLE OF CO2
In GTL
Recycling
ecyc g improves
p o es Ca
Carbon
bo -efficiency
e c e cy via
a co
conversion
e s o to CO
In Methanol
59
CO2 UTILIZATION
3.0
2.0
1.0
0.8
0.5
1
1.5
2
CO2 /C Ratio in Feed (mol / mol)
60
CO2
Flash Gas
CW
Purified Syngas
LP Flash
CO2 Stripper
Raw
Syngas
Absorber
MP Flash
CW
61
XTL Fundamentals, 1-3 Dec, 2009, Cape town
PRESENTATION OVERVIEW
Introduction
Syngas specifics for GTL
Syngas Routes and Technologies
Challenges and Options in optimizing Syngas
generation
Brief Scouting Comparison
Innovative Developments
Conclusions
62
XTL Fundamentals, 1-3 Dec, 2009, Cape town
CO2 Management
Process and effluent water treatment / reuse
O
Overall
ll water
t balance
b l
and
d treatment
t t
t esp. with
ith solid
lid feeds
f d
63
Typical targets
C-efficiency
> 75 80% + (Tail gas management)
Thermal efficiency > 60 70% + (Enhanced energy integration)
Capital index
64
65
No Stagnation
66
6767
Energy Integration
68
Power
export
Syngas
Generation
(SMR)
Endothermic
(external combustion)
Syngas
F-T
Synfuels
Synthesis
Exothermic
69
ASU
Waste heat
recovery
(process gas)
O2
NG
Syngas
Generation
(ATR)
Reaction heat
recovery
Syngas
Psuedo-adiabatic
Psuedo
adiabatic
Internal combustion
F-T
Synfuels
Synthesis
Exothermic
70
Off-gas fuel
Distillation unit
FT
reaction
water
Secondary
treatment
Air
Tertiary
treatment
Cooling
water
make-up
Effluent
71
PRESENTATION OVERVIEW
Introduction
Specifics of Syngas for GTL
Syngas Routes and Technologies
Ch ll
Challenges
and
d Options
O ti
in
i optimizing
ti i i Syngas
S
generation
ti
Brief Scouting Comparison
Innovative Developments
Conclusions
72
COMPARATIVE SUMMARY
(FEED
: LIGHT NG,, CN =104))
(
SMR
SMR +
OBSR
ATR
POx
2.7
1.5
1.4
0.2
NA
0.48
0.64
0.64
H2/CO
4.8
3.0
2.3
1.9
Yes
(+ external)
Yes
Partial
(<30%)
No
(H2-CO2)/(CO+CO2)
2.6
2.0
1.7
1.7
3.3
1.8
0.3
0.15
6.9
7.6
3.5
2.3
73
BALL
BALL
PARK ASSESSMENT OF SYNGAS ROUTES
Case
1
POx +
SMR
kg/bbl
NG feed,
feed
Gcal/bbl
C-efficiency
%
1), kg/bbl
Syngas
y g
g
CO impact, kg/bbl
2
Relative ranking 2)
2
ATR
SMR +
POx +
GHR +
EHTR
2.2
OBS
0.9
2.5
0.9
OBS
1.4
230
210
170
190
160
25
2.5
23
2.3
21
2.1
22
2.2
75
2.4
2
4
78
76
80
81
550
605
590
570
600
190
150
120
105
100
Base 4
1-2
1-2
74
PRESENTATION OVERVIEW
Introduction
Specifics of Syngas for GTL
Syngas Routes and Technologies
Ch ll
Challenges
and
d Options
O ti
in
i optimizing
ti i i Syngas
S
generation
ti
Brief Scouting Comparison
Innovative Developments
Conclusions
75
INNOVATIVE DEVELOPMENTS
Syngas
y g
GTL
76
77
CATALYTIC POX
PROs
CONs
78
79
O2 / N2 Selecttivity
10000
Membrane
Utopia
p
100
100
10000
Relative Oxygen Flux
1000000
80
e-
CO + 2H2
CH4 + O22e-
O2 (air)
Depleted Air
O2CO + 2H2 +
F d
Feed
CH4
Steam
Reforming
catalyst
O2 + 4e-
2O2-
eO2-
O2 (air)
( i)
Air
Reduction
catalyst
81
Syngas
y g
82
Ceramic membranes
Plasma process
83
p
CompactGTL
Velocys
Steam reforming
Fischer tropsch
Nippon GTL
CO2 reforming
g
Aimed at natural gas feedstocks with high CO2 levels
84
MATERIALS OF CONSTRUCTION
New alloys
N
ll
Better understanding of existing materials
85
Lab facilities
Catalysts
Ca
a ys s
Process conditions
Materials of construction
Commercial plants
86
CARBON EMISSIONS
S
Source:
DG
Gray 2002
XTL Fundamentals, 1-3 Dec, 2009, Cape town
87
PRESENTATION OVERVIEW
Introduction
Specifics of Syngas for GTL
Syngas Routes and Technologies
Ch ll
Challenges
and
d Options
O ti
in
i optimizing
ti i i Syngas
S
generation
ti
Brief Scouting Comparison
Innovative Developments
Conclusions
88
CONCLUSIONS
Capital
C
it l costt
Energy input
Environmental impact
89
CONCLUSIONS
90
ORYX,, QATAR
Q
34,000
bpd
34 000 b
d
0.32 Bcfd Natural g
gas
0.8 Bcfd Syngas
91