003 - Syngas Generation For GTL PDF

Syngas Generation
for
Gas
G to Li
Liquids
id (GTL)
XTL Fundamentals
1-3 December 2009
2009, Cape town
PRESENTER : SANJIV RATAN
Chief Technology Officer, Hydrogen-Syngas

Hydrogen Syngas Product Line &
Technologies, TECHNIP Group
Technip is among the top 5 global engineering contracting
company
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
XTL Fundamentals, 1-3 Dec, 2009, Cape town
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
Introduction
Syngas specifics for GTL
Syngas Routes and Technologies
generation
Conclusions
INTRODUCTION
The Gas in Gas-to-Liquid connotation has transitioned

since
i
its
it inception
i
ti
Originally in the 50s, Gas basically signified SynGas (derived

mainly from coal) for producing liquid fuels
In recent GTL terms, Gas refers to Natural Gas as being the
starting source for producing the Syngas
Within its portfolio, distinctive domains of Coal-to-Liquid (CTL)
and Biomass-to -Liquid (BTL) have evolved based on their starting
source with Syngas being the common bridge in the XTL family
source,
Also presently liquid tends to include, apart from more customary
F-T p
products,, also Methanol and other derivatives like DME
SYNGAS--BASED PRODUCTS OVERVIEW

SYNGAS
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
GTL (& GTC) SPECTRUM
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
Underlying objective of lowering

Total Chain Emissions (CO2, NOx & PM10)
per KM ( Well to Wheel )
per KW ( Well
Well to Wire
Wire )
GTL PROCESS SECTIONS

Air
S
Separation
i
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
Introduction
generation
Conclusions
SYNGAS SPECIFICS FOR GTL
Syngas denotes mixture of H2 and CO in various

proportions
For a given NG feedstock, the H2/CO ratio can vary in the
range of 1.8 to 5.0, depending upon the process /
technology applied
For F-T, the required ratio is ~ 2.0 with minimized level of CO2
and inerts
The syngas components H2 and

Th
d CO provide
id the
h H and
dC
elements required for producing the straight chain
Hydrocarbon liquids,
liquids while O ends up as H2O and CO2
SYNGAS is inherent to XTL
10
SYNGAS SPECIFICS FOR GTL
Choice of Syngas technology for GTL gets critical in view of :
For 10,000 bpd, it needs ~ 250 mmscfd Syngas
Economy of scale v/s cost-effective scale-up

Steam-power / energy integration (energy efficiency)
Level of investment (capital efficiency)
~100 mmscfd NG (1 TCF over 30 years)
Syngas generation for GTL is energy and capital intensive
Syngas dictates ~ 2/3rd of the specific energy usage

Accounts for more than half of the total investment
11
CHEMISTRY OF F-T SYNGAS
Basic F-T reactions (GTL)

(
)
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
(2n+1) H2 + n CO = CnH2n+2 + n H2O (Paraffins)

2n H2 + n CO
= CnH2n
+ n H2O (Olefins)
2
2n H2 + n CO
= CnH2nOH + n H2O (Alcohols)
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
(H2 - CO2 ) / (CO + CO2) ~2.0
12
INFLUENCE OF FF-T CATALYST ON SYNGAS
e cata
yst
Fe
catalyst
CO catalyst
In-situ WGS activity more suitable for heavier HC feeds

(lower H2/CO syngas)
N
Non-regenerable
bl
Low shift activity favors lighter HC feed (NG) based on

higher H2/CO
Higher selectivity for linear HC
Temperature (and pressure) sensitivity
Operating conditions
Higher T and lower P favors

f
lighter product slate
13
TYPICAL GTL SCHEME AND CC-BALANCE
Steam
Air
O2
Tail gas
F-T Synthesis
& Separation
Generation
H2
Proc. Cond
Power
Fuel gas / wash purge
Natural gas Syngas
Fl gas
Flue
Water
Steam
System
Air
Separation
Steam-Power
system
Reac. water
C, tph (50 kbpd) ~ 300
PSA
~ 70
Products
Work-Up
H2
Synfuels
H2 plant
~ 230
14
GTL INTEGRATION SUB

SUB--SYSTEMS (SMDS)
Air
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
Water & Oxygenates
H2/CO = 1.76
Fischer-Tropsch
Fi
h T
h
Reactor
Middle
Distillate
H2/CO = 2.10
15
Introduction

Challenges and Options in optimizing Syngas generation
Conclusions
16
SYNGAS ROUTES AND TECHNOLOGIES
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
Traditionally non-catalytic Partial oxidation (POx)

Steam + O2
Sub-stoichiometric combustion of HC with Oxygen
at much higher temps (1200-1400 C)
CH4 + O2 = 2 H2 + CO (NG feed ; - 39 kJ/mole)
Recent developments over catalytic POx (CPO)
CO Contributor ; Hydrogen deficient for F-T
17
SYNGAS ROUTES AND TECHNOLOGIES
Auto-thermal
Auto
thermal reforming (ATR)
Partial oxidation with oxygen and steam carrying in-situ SMR

Catalytic with 900-1100 C outlet (typically 1050 C)
2 CH4 + H2O + O2 = 5 H2 + 2 CO
H2/CO =2.5
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
Combination / Hybrid Routes
Combination of SMR with POx and ATR in parallel or series to get

the specific benefits for GTL (syngas) applications
18
WAYS TO ADJUST H2/CO RATIO IN SYNGAS

Decreases
Ratio
R ti
Lower S/C ratio /
High severity reforming
H2 skimming using
Membranes
Recycle Process CO2
Import CO2 /
F-T tail gas recycle
Shift Conversion
Process combination
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
H2/CO RATIO REGIMES

Feed : Natural Gas; CN =1.05
O2 / C
ratio
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
with import CO2
20
SYNGAS TECHNOLOGIES OVERVIEW
Steam Reforming
(SMR)
Conventional SMR
Compact reforming
Regenerative reforming*
Partial Oxidation (POx)
Non catalytic
Catalytic
Autothermal Reforming (ATR)
Combination Routes
Fixed bed adiabatic

Oxygen blown
Air blown
Fluidised
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
Non catalytic
Catalytic
Combination Routes
Fixed bed adiabatic

Oxygen blown
Air blown
Fluidised
Combi reforming
SMR + ATR in
i split
li -parallel
ll l
2-step reforming
SMR + ATR (
(OBS)) in series
Combi Pox
22
CONVENTIONAL STEAM REFORMING

Flue gas
15
Fuel
180
Steam
Steam
Reforming duty
100
150 C
1100 C
Steam
880 C
Air
300 C Syngas
30
Excess S/H steam
45
Feed
10
23
STEAM REFORMING (SMR)

Feed inlet system
Combustion Air
Burners
Catalyst tubes
Outlet system
Flue Gas
T
Tunnels
l
Transfer Line
Reformed
gas
24
STEAM REFORMING PRINCIPLES
Temp
perature Deg C
Fuel / air
gas/
steam
800
CH4 + H2O CO + 3H2 Endo
600
CO + H2O CO2 + H2 Exo

400
200
0.2
0.4
0.6
Fraction down tube
0.8
Gas Temp Eq'm Temp
catalyst
a e
flame
tube
Nat. gas + steam flow down vertical tubes at pressure

Fuel combusted at atm. pressure in external furnace
Radiant Heat transfer to tubes
Catalyst shaped to enhance inside-tube heat transfer
Furnaces can be cylindrical (small), top-fired or side-fired
(terrace- wall)
Close approach to methane-steam equilibrium at high
exit temperature
25
STEAM REFORMING
PROs
Simple,
Simple highly proven
Reliable and flexible
No need for Oxygen
Cost-effective (esp. for H2/CO >3 on NG)
CONs
Higher H2/CO and CO2/CO ratios
ratio adjustment using membranes
Reforming pressure typically limited to < 40 bar

Max economical unit size of ~300 mmscfd syngas
Max.
(equiv. to ~12,000 bpd)
Little stretch possible using Pre-reforming

Pre reforming
26
Steam Reforming
(SMR)
Conventional SMR
Compact reforming
Non catalytic
Catalytic
Combination Routes
Fixed bed adiabatic

Oxygen blown
Air blown
Fluidised
Combi reforming
SMR + ATR in
i split
li -parallel
ll l
2-step reforming
SMR + ATR (
(OBS)) in series
Combi Pox
27
PARTIAL OXIDATION PROCESSES
Conventional (non-catalytic) partial oxidation (POx)
Catalytic partial oxidation
Non-equilibrium based
E ilib i
Equilibrium
based
b d
28
CONVENTIONAL PARTIAL OXIDATION (POX

POX))
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
Residues, petroleum coke, coal
Allows higher
g
pressure
p
syngas
y g (upto
( p 60 bar))
CONs
Large Oxygen usage (~3500 tpd for 15,000 bpd)

Reliability (especially on heavier feeds)
Needs supplemental hydrogen for F-T (H2/CO << 2)
Capital efficiency
Limited scale-up compared to SMR
Need for more trains

31
CATALYTIC PARTIAL OXIDATION
oxygen
feed g
gas
fuel gas
CPO
steam
syngas
CPO operates at 900-1000C

(very
high
and
(
h h space velocity
l
d
flameless)
Feed gas preheated (possibly
pre-reformed)
Little or no steam addition
Medium oxidant consumption
(usually O2)
Theoretical H2/CO ratio 2
Low CO2, low CH4 in syngas
Better selectivity than noncatalytic Pox
Non-equilibrium reforming
No commercial scale
application
pp
so far
32
CATALYTIC PARTIAL OXIDATION
PROs
Most ideal gas composition for FT

Low CH4 and CO2 in syngas
High efficiency
Small reactors and catalyst volumes
CONs
Developing process, not commercially proven

Sophisticated reactor designs
Novel catalysts
Requires oxygen
33
SYNGAS GENERATION TECHNOLOGIES
Steam reforming (SMR)
Conventional SMR
Compact Reforming
Pre-reforming
Non catalytic
Catalytic
Autothermal reforming (ATR)
Fixed Bed Adiabatic

Oxygen blown
Air blown
Fluidised
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
Tail gas Recycle

FT
synthesis
100 MMSCFD feed gas ~ 265 MMSCFD H2 + CO
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
ATR: S/C RATIO SENSITIVITY

O2/C ratio
:
0.64
Outlet temperature : 1050 (C)
Outlet pressure
: 35 bar abs
y
No CO2 recycle
S/C ratio (molar)
1.7
1.2
0.6
Residual methane
0.30
0.48
1.05
CO2 in dry syngas
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
Provides H2/CO ~2.0
with partial CO2 recycle and reduced S/C ratio
Allows high pressure reforming (up to 50 bar)

Well proven in ammonia and methanol
CONs
Need for oxygen (3,600 tpd for 20,000 bpd)

Heat integration in important
Limited references on GTL conditions (burner design)
Maximum current size equivalent to ~17
~17,000
000 bpd
38
ORYX ATRATR-BASED SYNGAS SECTION
39
AIR--BASED ATR
AIR
Was launched by Syntroleum
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
Much larger downstream equipment owing to handling large

nitrogen volume and its dilution effect
Relative power consumption
Limitation on tail gas recycle or efficient usage
Less flexibility in design
40
FLUIDISED AUTOTHERMAL REFORMING
Developed by ExxonMobil
PROs
CONs
Scaleable to high capacities

Based on FCC experience
Severe catalyst operating regime

Possibly complex operation and controls
Complications of dust, attrition, erosion etc
Process believed to have been abandoned
41
H2/CO RATIO V/S CO YIELD
%C0YIELD
SMR
70
85
92
96
100
ATR
POX
COPOX
IDEAL
24
2.4
1.8
1.9
2.1
42
SYNGAS GENERATION TECHNOLOGIES
Steam reforming (SMR)
Conventional SMR
Compact Reforming
Pre-reforming
Non catalytic
Catalytic
TL Fundamentals, 1-3 Dec, 2009, Cape town
Autothermal reforming (ATR)
Fixed Bed Adiabatic

Oxygen blown
Air blown
Fluidised
Hybrid processes
Combined Reforming
Gas Heated Reforming (GHR)*
EHTR Post Reforming
POX+EHTR
43
HYBRID PROCESSES
Combi reforming :
SMR + ATR in split - parallel
2-step reforming :
SMR + ATR (OBS) in series

Combi POx
POx + SMR in independent mode

POx / ATR + EHTR* in split-parallel
Hybrid processes combine the benefits of each process

and offer higher integration potential
but consequently suffer from increased complexity
complexity.
44
COMBI REFORMING
A combination of a steam reformer and an autothermal

reformer
Around 1/3rd of the reforming duty is done on the steam
reformer and the balance on the ATR. This maximizes
production compared to an ATR on its own and the steam
reformer is relatively small
Since combined reforming has both an ASU and a steam
reformer
f
the
h overallll system is
i more complex
l and
d this
hi can
affect reliability
45
COMBI REFORMING
PROs
Established technology for methanol

Hi h single
High
i l stream
t
capacity
it ~20,000
20 000 bpd
b d
CON
CONs
More complex than steam reforming or ATR alone

Requires oxygen
Steam ratio and therefore H2 : CO ratio higher than ideal for GTL
46
LURGI'S COMBI
COMBI--REFORMING
47
TWO-- STEP REFORMING

TWO
Oxygen Blown Secondary Reformer (OBSR) downstream

Stea
eo e
Steam Reformer
Advantages :
Closer H2/CO ratio for GTL

Converts part of the feed (25 to 40%)
Significant reduction of the duty of the Reformer
Carbon formation potential in OBS suppressed due to presence of
sufficient
ffi i
H2
Technology Status
Process combustion followed by SMR step

Endothermic reaction heat supplied by combustion
Proven
~ 400 MMSCFD Syngas ( ~17,000 bpd ) with single OBSR unit
Can be combined with pre

pre-reforming
reforming and CO2 recycle to
achieve the desired H2/CO ratio
48
TWO STEP REFORMING
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
L Fundamentals, 1-3 Dec, 2009, Cape town
Hydrodesulphurizer
ZnO bed
to Heat Recovery
49
SYNGAS ROUTE AND PLAYERS OVERVIEW

Syngas Route
Steam Reforming (SMR)
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
: Shell (SGP*) + SMR /
Fixed bed
Air Blown
Fluidised
Combi
:
:
:
:
: Conoco (CoPOx)*
Topsoe*-Sasol-Chevron
Syntroleum*
Syntroleum
ExxonMobil *
Lurgi * / GTL F-1
(A)GHR* + OBS : Johnson Matthey

EHTR* + Pox
: Technip-Air Products +
50
ADVANCES IN SMR SYNGAS ROUTES
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
Reduction in steam generation against fuel savings
Smaller reformer and steam system
Configurations
z
2 iin -1
1 outt
Enhanced
Heat Transfer Reformer (EHTR )
2 in - 2 out
Advanced
Gas Heated reformer (AGHR)
51
REGENERATIVE REFORMING : EHTR

Feed + Steam
Enhanced Heat
Transfer Reformer
2 iin - 1 outt
Hot reformed gas

Source
Total reformed gas to
heat recovery
52
EHTR DESIGN AND FABRICATION
53
SMR--EHTR INTEGRATION
SMR
Process
Steam
Enhanced Heat Transfer

Reformer (EHTR)
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
POX + EHTR FLOWSHEET
Start-up Steam
Figure-2B : Simplified Process Flow Scheme for

70,000 bpd Alternative GTL-Complex
837 Gcal/hr
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
((Heavyy Paraffin Conversion))
(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
GAS HEATED REFORMING + ATR IN SERIES
PROs
High carbon and thermal efficiency

High single stream capacity ~15,000 bpd
Smaller recycle systems
Simplified steam and water systems
Simple FT water treatment options
CONs
Not commercially proven on GTL applications

Materials of construction issues require further development
57
GAS HEATED REFORMING + ATR IN SERIES
Heat recycle to feed

Process without
power export & low
CO2 emissions
h
l
Being developed at steam ratio of 1.0 with recycle CO2
and/
d/ or FT ttail-gas
il
oxygen
feed gas
syngas
58
ROLE OF CO2
In GTL
Inactive form of carbon for F-T hydrocarbon products

Allowable level in syngas
Lower for Fe-based F-T catalyst (Shift activity)

Slightly higher for Cobalt catalyst; lower temperature
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
Active form of carbon
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 REMOVAL (BASF A-MDEA PROCESS)
CO2
Flash Gas
CW
Purified Syngas
LP Flash
CO2 Stripper
Raw
Syngas
Absorber
MP Flash
CW
61
Introduction
generation
Conclusions
62
CHALLENGES ON SYNGAS FOR GTL
Process optimization for achieving the required H2/CO ratio

with light HC feed like NG
Minimized level of inerts and contaminants
Methane + Nitrogen content (esp

(esp. with recycle streams)
Level of CO2 removal / recycle and its integration
Other contaminants analysis

y and handling
g when using
g solid
feedstocks
Environmental aspects
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
CHALLENGES ON SYNGAS FOR GTL
High degree of tailored reliability

Heat & power integration
Energy intensity within process (mainly ASU)

Tailored steam-power combined cycle
Cost-effectiveness against current / conventional fuels
Economy of (large) scale ~ 400 kNm3/h syngas for 17

17,000
000 bpd
Capital efficiency break-point for multiplicity of equipment
Typical targets
C-efficiency
> 75 80% + (Tail gas management)
Thermal efficiency > 60 70% + (Enhanced energy integration)
Capital index
< 70,000 $/bpd for 50,000 bpd core GTL plant
64
CHALLENGES FOR EQUIPMENT
Very large capacity equipment
Combating potential metal dusting
Building block approach

Benchmark scale-up limits
Optimum layout based on multiple trains
Co b ed severity
Combined
se e ty o
of co
composition
pos t o ((high
g % CO) with
t high
g Temp
e p&
pressure
Multiplicity of equipment against economy of scale and

l t layout
cluster
l
t
65
HYDRAULICS USING CFD MODELING
No Stagnation
Ensuring better performance

Higher plant reliability
Lower life cycle costs
Flue gas tunnel
66
MODULARIZATION AND PREPRE-FABRICATION

Considerations
Site conditions
z Overall schedule
z Site labor situation
z Transport
z Cost-effectiveness
z
6767
Energy Integration
68
GTL ENERGY (MIS) MATCH : SMR
Power
export
Waste heat recovery

Process gas and Flue gas
NG
Syngas
Generation
(SMR)
Endothermic
(external combustion)
Syngas
Reaction heat recovery
F-T
Synfuels
Synthesis
Exothermic
69
GTL ENERGY (MIS

(MIS)) MATCH : ATR
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
TYPICAL REACTION WATER

TREATMENT SYSTEM
Off-gas fuel
Distillation unit
FT
reaction
water
Secondary
treatment
Air
Tertiary
treatment
Cooling
water
make-up
Effluent
71
Introduction
Specifics of Syngas for GTL
Ch ll
Challenges
and
d Options
O ti
in
i optimizing
ti i i Syngas
S
generation
ti
Conclusions
72
COMPARATIVE SUMMARY
(FEED
: LIGHT NG,, CN =104))
(
SMR
SMR +
OBSR
ATR
POx
Steam / Carbon (molal)
2.7
1.5
1.4
0.2
Oxygen / Carbon (molal)
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
Residual Methane (% vol.

d basis)
dry
b i )
3.3
1.8
0.3
0.15
% CO2 in dry Syngas
6.9
7.6
3.5
2.3
Process CO2 Recycle

(for achieving H2/CO~ 2)
73
BALL
BALL
PARK ASSESSMENT OF SYNGAS ROUTES
Case
1
POx +
SMR
S/C for SMR

Oxygen
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
1) H2/CO ~2, max. inerts ~8% vol. dry

2) Based on Opex + Capex
Full Heat Integration
74
Introduction
Ch ll
Challenges
and
d Options
O ti
in
i optimizing
ti i i Syngas
S
generation
ti
Conclusions
75
INNOVATIVE DEVELOPMENTS
Syngas
y g
CO2 - methane (dry) reforming

Compact Reformer
Catalytic POx (CPO)
Ion-transport ceramic membranes (ITM) for O2 generation as well
as direct syngas production
GTL
More active and selective F

F-T
T catalysis
FPSO systems for localized (smaller) scale units
Direct liquids from hydrocarbon pyrolysis
76
BP--DAVY COMPACT REFORMER

BP
Steam raising eliminated

Modular fabrication and
transportation
Bundle fits standard
container
Small footprint (25% of
conventional Steam
Reformer)
Maximum
a
u capacity
apa y 2500
500
bpd
Multiple units
77
CATALYTIC POX
PROs
Ideal gas composition for FT

Small reactors and catalyst volumes
Lower temperatures with low CH4 and CO2 in syngas
High efficiency
CONs
Not commercially proven (COP pilot unit)

Sophisticated reactor designs
N
Novel
l catalysts;
t l t U
Unconventional
ti
l regime
i
78
ION TRANSPORT MEMBRANE (ITM)

FOR OXYGEN GENERATION
79
ION TRANSPORT MEMBRANE
O2 / N2 Selecttivity
10000
Membrane
Utopia
p
100
Polymer Upper Bound

1
1
100
10000
Relative Oxygen Flux
1000000
30% to 50% Cost Reduction

80
ITM FOR SYNGAS FROM NG :

A BREAKTHROUGH
Syngas
S
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
US DOE Project (1997

(1997--2005) involving Air Products, ARCO, Chevron, Babcock
[Oxygen Transport Membrane (OTM) alliance of Sasol,
Sasol, BP Amoco, Praxair, Statoil is dissolved]
81
ITM SYNGAS CAPITAL COST REDUCTION
Syngas
y g
Air Products & Chemicals Inc.
82
NOVEL SYNGAS PROCESSES
Ceramic membranes
Plasma process
Potential for reduced cost air separation

Combined directly with partial oxidation/reforming
At research stage
At small scale
Direct oxidation to products (e.g. methanol, gasoline)
Bypasses syngas formation step completely

Yields and selectivities very low
If low temperature process then heat utilisation difficulties
83
NOVEL GTL PROCESSES
p
CompactGTL
Compact multi-channel reactors
Compact integrated processes for offshore use

Aimed at associated gases to facilitate oil production
operations
ti
without
ith t fl
flaring
i
Velocys
Steam reforming
Fischer tropsch
Compact channel reactors
Nippon GTL
CO2 reforming
g
Aimed at natural gas feedstocks with high CO2 levels
84
MATERIALS OF CONSTRUCTION
Corrosion has always been a problem with syngas plants

Limited or manageable with conventional plants at high
steam ratios
More severe at steam ratios of about 2
Can be very severe at steam ratios of 1 or less
Problems generally appear in cooling trains downstream of
reformers
Specific
p
operating
p
g conditions are important
p
Development programmes continuing to find improved
solutions
New alloys
N
ll
Better understanding of existing materials
85
SYNGAS PROCESS DEVELOPMENT NEEDS
Lab facilities
Pilot scale testing
Feed conversion and yield

Recycle effects and options
Demo scale units
Catalysts
Ca
a ys s
Process conditions
Materials of construction
Catalysts and equipment

p
performance
Operational testing
Material feedback
Commercial plants
New lessons learned
86
CARBON EMISSIONS
S
Source:
DG
Gray 2002
87
Introduction
Ch ll
Challenges
and
d Options
O ti
in
i optimizing
ti i i Syngas
S
generation
ti
Conclusions
88
CONCLUSIONS
Cost-effective monetization of stranded NG is key driver GTL

Syngas generation constitutes a major portion of a GTL
complex
Capital
C
it l costt
Energy input
Environmental impact
GTL units above 17-22,000 bpd generally exceed current

size limits of front-end
front end units and require multiple trains
Though syngas technology is mature, advanced and
g developed
p to respond
p
innovative solutions are still being
effectively to the emerging needs and challenges
89
CONCLUSIONS
Syngas technology though matured, calls for advanced

solutions, esp. for larger units for effectively responding to
the emerging needs and challenges.
Even with relatively cheap gas, it requires judicious steampower synergy for improving the capital efficiency, economic
viability
i bili and
d HSE compliance
li
Future innovations are poised towards lower cost Oxygen,
higher C and energy efficiencies and lower CO2 footprint
Syngas
90
ORYX,, QATAR
Q
34,000
bpd
34 000 b
d
0.32 Bcfd Natural g
gas
0.8 Bcfd Syngas
91

003 - Syngas Generation For GTL PDF

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Syngas Generation

PRESENTER : SANJIV RATAN

Chief Technology Officer, Hydrogen-Syngas

XTL Fundamentals, 1-3 Dec, 2009, Cape town

XTL Fundamentals, 1-3 Dec, 2009, Cape town

XTL Fundamentals, 1-3 Dec, 2009, Cape town

The Gas in Gas-to-Liquid connotation has transitioned

Originally in the 50s, Gas basically signified SynGas (derived

XTL Fundamentals, 1-3 Dec, 2009, Cape town

SYNGAS--BASED PRODUCTS OVERVIEW

XTL Fundamentals, 1-3 Dec, 2009, Cape town

GTL (& GTC) SPECTRUM

Underlying objective of lowering

GTL PROCESS SECTIONS

XTL Fundamentals, 1-3 Dec, 2009, Cape town

SYNGAS SPECIFICS FOR GTL

Syngas denotes mixture of H2 and CO in various

The syngas components H2 and

SYNGAS SPECIFICS FOR GTL

Choice of Syngas technology for GTL gets critical in view of :

For 10,000 bpd, it needs ~ 250 mmscfd Syngas

Economy of scale v/s cost-effective scale-up

Syngas generation for GTL is energy and capital intensive

Syngas dictates ~ 2/3rd of the specific energy usage

XTL Fundamentals, 1-3 Dec, 2009, Cape town

CHEMISTRY OF F-T SYNGAS

Basic F-T reactions (GTL)

(2n+1) H2 + n CO = CnH2n+2 + n H2O (Paraffins)

XTL Fundamentals, 1-3 Dec, 2009, Cape town

(H2 - CO2 ) / (CO + CO2) ~2.0

INFLUENCE OF FF-T CATALYST ON SYNGAS

In-situ WGS activity more suitable for heavier HC feeds

Low shift activity favors lighter HC feed (NG) based on

Higher T and lower P favors

XTL Fundamentals, 1-3 Dec, 2009, Cape town

TYPICAL GTL SCHEME AND CC-BALANCE

Fuel gas / wash purge

Natural gas Syngas

C, tph (50 kbpd) ~ 300

XTL Fundamentals, 1-3 Dec, 2009, Cape town

GTL INTEGRATION SUB

Water & Oxygenates

XTL Fundamentals, 1-3 Dec, 2009, Cape town

Syngas specifics for GTL

Syngas Routes and Technologies

XTL Fundamentals, 1-3 Dec, 2009, Cape town

SYNGAS ROUTES AND TECHNOLOGIES

Traditionally non-catalytic Partial oxidation (POx)

XTL Fundamentals, 1-3 Dec, 2009, Cape town

SYNGAS ROUTES AND TECHNOLOGIES

Partial oxidation with oxygen and steam carrying in-situ SMR

Combination / Hybrid Routes

Combination of SMR with POx and ATR in parallel or series to get

XTL Fundamentals, 1-3 Dec, 2009, Cape town

WAYS TO ADJUST H2/CO RATIO IN SYNGAS

H2/CO RATIO REGIMES

with import CO2

SYNGAS TECHNOLOGIES OVERVIEW

Partial Oxidation (POx)

Autothermal Reforming (ATR)

XTL Fundamentals, 1-3 Dec, 2009, Cape town

Fixed bed adiabatic