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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

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

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

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

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

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

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

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

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
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

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

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

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

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

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

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

(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

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

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

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

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

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

15

PRESENTATION OVERVIEW

Introduction

Syngas specifics for GTL

Syngas Routes and Technologies


Challenges and Options in optimizing Syngas generation
Brief Scouting Comparison
Innovative Developments
Conclusions

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

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

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

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

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

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

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

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

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

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

SYNGAS TECHNOLOGIES OVERVIEW

Steam Reforming
(SMR)

Conventional SMR
Compact reforming
Regenerative reforming*

Partial Oxidation (POx)

Non catalytic
Catalytic

Autothermal Reforming (ATR)

Combination Routes

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

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

23

STEAM REFORMING (SMR)


Feed inlet system
Combustion Air

Burners
Catalyst tubes

Outlet system

Flue Gas
T
Tunnels
l
Transfer Line

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

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

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

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

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

26

SYNGAS TECHNOLOGIES OVERVIEW

Steam Reforming
(SMR)

Conventional SMR
Compact reforming
Regenerative reforming*

Partial Oxidation (POx)

Non catalytic
Catalytic

Autothermal Reforming (ATR)

Combination Routes

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

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
27

PARTIAL OXIDATION PROCESSES

Conventional (non-catalytic) partial oxidation (POx)

Catalytic partial oxidation

Non-equilibrium based
E ilib i
Equilibrium
based
b d

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

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

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

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

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

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

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

CATALYTIC PARTIAL OXIDATION

oxygen

feed g
gas

fuel gas

CPO

steam

syngas

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

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

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

33

SYNGAS GENERATION TECHNOLOGIES

Steam reforming (SMR)

Conventional SMR
Compact Reforming

Pre-reforming

Partial Oxidation (POx)

Non catalytic
Catalytic

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

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

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

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

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

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

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

38

ORYX ATRATR-BASED SYNGAS SECTION

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

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

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

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

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

41

H2/CO RATIO V/S CO YIELD

%C0YIELD

SMR

70

85
92
96
100

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

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

Partial Oxidation (POx)

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


GHR* + 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
XTL Fundamentals, 1-3 Dec, 2009, Cape town

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

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

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

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

46

LURGI'S COMBI
COMBI--REFORMING

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

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

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

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)

Partial Oxidation (POx)

Auto-Thermal
Auto
Thermal Reforming
(ATR)
Regenerative reforming +
O2-based

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

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)

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

51

REGENERATIVE REFORMING : EHTR


Feed + Steam

Enhanced Heat
Transfer Reformer

2 iin - 1 outt

Hot reformed gas


Source
Total reformed gas to
heat recovery
XTL Fundamentals, 1-3 Dec, 2009, Cape town

52

EHTR DESIGN AND FABRICATION

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

53

SMR--EHTR INTEGRATION
SMR

Process
Steam

Enhanced Heat Transfer


Reformer (EHTR)

Desulphurization

HC feed

Primary
reformer

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

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

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

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

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

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

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

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

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

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

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

59

CO2 UTILIZATION

3.0

2.0

1.0
0.8

0.5

1
1.5
2
CO2 /C Ratio in Feed (mol / mol)

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

60

CO2 REMOVAL (BASF A-MDEA PROCESS)

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

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

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

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

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

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

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

65

HYDRAULICS USING CFD MODELING

No Stagnation

Ensuring better performance


Higher plant reliability
Lower life cycle costs

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

Flue gas tunnel

66

MODULARIZATION AND PREPRE-FABRICATION


Considerations
Site conditions
z Overall schedule
z Site labor situation
z Transport
z Cost-effectiveness
z

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

6767

Energy Integration

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

68

GTL ENERGY (MIS) MATCH : SMR

Power
export

Waste heat recovery


Process gas and Flue gas
NG

Syngas
Generation
(SMR)

Endothermic
(external combustion)

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

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

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

F-T
Synfuels
Synthesis

Exothermic
70

TYPICAL REACTION WATER


TREATMENT SYSTEM

Off-gas fuel
Distillation unit
FT
reaction
water

Secondary
treatment

Air

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

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

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

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)

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

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

Full Heat Integration

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

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

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

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

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

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

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

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

78

ION TRANSPORT MEMBRANE (ITM)


FOR OXYGEN GENERATION

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

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


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

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]

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

81

ITM SYNGAS CAPITAL COST REDUCTION

Syngas
y g

Air Products & Chemicals Inc.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

90

ORYX,, QATAR
Q

34,000
bpd
34 000 b
d
0.32 Bcfd Natural g
gas
0.8 Bcfd Syngas

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

91