Lurgi MegaMethanol Technology –

Delivering the building blocks for future

fuel and monomer demand

Presented at the DGMK Conference

„Synthesis Gas Chemistry“, October, 4. – 6., 2006

Dr. Thomas Wurzel, Lurgi AG

Agenda

Motivation

Today´s methanol industry

Towards larger capacities – a joint effort of R&D, catalyst

development and plant engineering

Monomer and fuel from Methanol

Conclusions

2
Increasing energy demand

Billion tons of coal equivalent

3 0
28
26
24
22
20
1 8
1 6
1 4
1 2
1 0
8
6
4
2
0
1970 198 0 1990 2 001 2 02 0 2 05 0





















3
 How will the future look like?

4
Sources:
www.spiegel.de/fotostrecke/0,5538,16327,00.html
http://www.pacificrenewables.com/fischer-tropsch.htm
Spoilt for feedstock choices

1380 hits

1110 hits 5
754 hits
Syngas & MeOH – the flexible dream team

Coal Chemicals
Natural Gas Propylene
BioMass DME
Tar Sands etc. Fuels

6
Syngas Methanol
Chemical Methanol Market

Today development
Formaldehyde 12 MM tpa up
MTBE 6 MM tpa down
Acetic Acid 3 MM tpa up
Miscellaneous Uses 11 MM tpa up
TOTAL 32 MM tpa

annual increase 3 % i. e. 1 MM tpa

pre-dominant feedstock: natural gas

close the gap in low cost methanol supply: MegaPlants (> 1 million tpy)

selection of syngas technology is key 60 – 65 % of ISBL cost

to economic methanol production
7
Ways to produce Syngas

Coal Heavy Naphtha LPG Refinery Natural Gas

Residue Off-gases

Pre- Pre-
reforming Tubular reforming
Reforming
Tubular Tubular
Gasification MPG MPG
Reforming Reforming

H2S H2S Secondary Autotherm.

Rectisol Rectisol Reforming Reforming

CO Shift CO2
Conversion Removal

PSA Cold Box

PSA

8
H2 H2 CO Synthesis Gas
H2/CO Ratios for Syngas Generation

S MR

C MR

A T R

MPG

1 2 3 4 5
H2/CO ratio
F e e d N atu ral G as CMR= Co m b i n e d Me t h a n e Re f o r m i n g

9
Typical Single-Train Capacities

Steam Reforming

Autothermal
Reforming
MPG- Partial
Oxidation

MeOH Reforming

100 1.000 10.000 100.000 1.000.000

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Lurgi Highlights for
Syngas Production

Lurgi offers all gas-b ased sy n gas t ec h n ologies

W orld largest sin gle t rain sy n gas un it ( A T LA S )

W orld largest m ult ip le t rain sy n gas un it ( M osselb ai)

H igh est out let t em p erat ure for a st eam reform er ( B P
S ic h uan p lan t )

V ast ex p erien c e in h an d lin g ox y gen ( sin c e 1 9 2 8 )

5 0 + y ears ex p erien c e in A T R ( sin c e 1 9 5 4 )

M ore t h an 1 0 0 , 0 0 0 , 0 0 0 N m 3 / d ay c ap ac it y in st alled

P ilot p lan t t o t est m ore sev ere op erat in g c on d it ion s

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Syngas Benchmarks for MeOH

Parameter Steam Autothermal Combined

Reforming Reforming Reforming

Stoechiometric 2.95 2.05 2.05

number, SN

CO/CO2 ratio 2.3 2.5 2.8

Methane slip, 3.28 1.76 2.10

% (dry)
-
Steam reformer 1740 460
duty, GJ/hr

Syngas flow at 43713 20240 19433

compressor
suction,
12
m3eff. / hr
Syngas Benchmarks for MeOH

Parameter Conventional MegaMethanol

Technology Technology

Capacity, MTPD 2500 5000

Natural gas 30 28.5

consumption
(MMBTU/ton MeOH)

Investment1), % 100 130

Operating cost, % 100 97

Production cost, % 100 79

1) Oxygen supply over the fence

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Preferred route: Oxygen-based

ATR: homogeneous/heterogeneous formation of syngas

principle reactions:

combustion of methane

steam reforming of methane

Water gas shift reaction

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Features of Autothermal Reformer

Low S/C ratio ≈ 1.5 - 0.5 mol/mol

high CO selectivity


low CO2 emission



Outlet temperature 950 - 1050 °C

Low methane slip


Close approach to equilibrium



Pressure: 40 bar realised (large scale)

70 bar realised Demoplant


High gas throughput possible

Up to 1,000,000 Nm3 gas /hr


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Reactor Design

uncooled burner (no CW circuit)

→ proper mixing and combustion
→ free of vibration

Burner and Reactor as one unit

no start-up burner

low SiO2 α-Al2O3 Nickel catalyst

→ high thermal stability

multilayer refractory lining

→ thermal protection

16
Development steps towards MegaSyn™

17

Atlas Methanol - 5000 mt/d, commissioned 2004

Milestones in ATR History

1922 Autothermal Reforming

(recuperative mode)

1928 Lurgi introduces oxygen-based gas production

(coal gasification)

1954 First Lurgi ATR (Towngas production)

1979 First application of combined reforming

2004 First MegaSyn Application in operation

(ATLAS plant)

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Development of Technology

Picture 1 – Towngas, Hamburg, 1954

Picture 2 – FT Syngas, Mosselbai, 1993

Picture 3 – MegaMethanol, ATLAS, 2004

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Towngas, Hamburg, 1954

Feedstock: Refinery Offgas

Product: Towngas
Capacity: 25.2 MMSCFD

20
PetroSA, Mosselbay, 1993

Feedstock: Natural Gas

Product: Fischer-Tropsch Syngas
Capacity: 252 MMSCFD per train 21
 ATLAS, Trinidad, 2004

Feedstock: Natural gas

Product: Methanol Syngas
Capacity: 420 MMSCFD 22
Base of Fluid Dynamical Simulation

Reactor/ Velocity
Thermo-chemical Navier-Stokes
Burner temperature
Model Equations
Geometry pattern

CFD was introduced approx. 15 years ago

in-house expert group established and growing

standard tool for design work

intensive model validation performed

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Advantages of Oxygen-based Syngas
Generation

Reduced investment (20 – 30 %) compared to conventional

steam reforming

Higher energy efficiency (less CO2 emissions)

Higher flexibility towards feedstock fluctuation

Availability of one single train plant is higher than of two

smaller trains

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The next generation:
HP POX Pilot Plant

Demonstrationplant for production of Syngas from Natural Gas, Liquid Hydrocarbons/Slurries25

at
pressures up to 100 bar sponsored by BMWA, SMWK, mg technologies
Development of Synthesis Loop
1. Conventional Synthesis Loop

Synthesis Gas
16 bar

Cooling Water

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Development of Synthesis Loop
Lurgi Steam Raising Reactor

• Quasi isothermal Operation

• Extremely quick transfer of Reaction Heat
• Methanol Yield up to 1.8 kg MeOH/l Catalyst
• Long Catalyst Operation Life
• 80 % of Reaction Heat converted to MP steam
• Safe and uniform Temperature Control
• Overheating of Catalyst impossible
• Thermosyphon Circulation - no Pumps
• Easy Start-up by direct Steam Heating
• Fast Load Changes possible
• Easy and fast Load/Discharge of Catalyst

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Development of Synthesis Loop
Temperature Profile Steam Raising Reactor

280

275

270
Temperature °C

265
Reaction
260
Cooling Water
255

250

245

240
0 0,2 0,4 0,6 0,8 1
Catalyst Height
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Development of Synthesis Loop
Steam Raising Reactors

Inter-
changer
Steam Drum

Reactors

29
 Development of Synthesis Loop
2. Two-Step Methanol Synthesis

Recycle Gas-cooled Steam Raising

Compressor Reactor Reactor
MP-Steam

Compressed Synthesis Gas

Purge Crude Boiler Feed

Gas Methanol Water 30
Development of Synthesis Loop
Lurgi‘s Two Reactor Concept (CMC)

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Development of Synthesis Loop
Gas Cooled Reactor

Large Single Train Capacity

Low Investment Cost
Operation at the Optimum Reaction
Route

High Equilibrium Driving Force

High Conversion Rate
Lowest recycle/syngas ratio
High methanol content (11 %) at
reactor outlet

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 Development of Synthesis Loop
Temperature Profile Gas Cooled Reactor

300

250
Temperature °C

200

Reaction
150
Cooling Gas

100

50

0
0 0,2 0,4 0,6 0,8 1
Catalyst Height

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Development of Synthesis Loop
Summary of Highlights / Two-Step Methanol Synthesis

Steam Raising Reactor Gas Cooled Reactor

g Simple and Exact Reaction Control g Operation at the

Optimum Reaction Route
g Quasi Isothermal Operation
High Equilibrium Driving Force
g High Methanol Yield


High Conversion Rate
g High Energy Efficiency


Heat of Reaction converted to MP steamg
Elimination of Reactor Feed Preheater
g
(80 %) g Elimination of Catalyst Poisoning
g Kinetically controlled g Thermodynamically controlled

 High SyngasConversion Efficiency

 Extended Catalyst Life (almost unlimited)
 Large Single Train Capacity
 Low Investment
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Development of Synthesis Loop
Synthesis Design Parameters

Conventional Two step

synthesis synthesis
Syngas Flow m3N/t MeOH 2580 2550

Recycle Flow m3N/t MeOH 8500 5100

Synthesis Loop Pressure bar 80 75

Methanol Content mol% 7 11

Reactor Outlet

The implementation of the MegaMethanol technology represents a unique joint effort

comprising technology development and catalyst research (Süd-Chemie)
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Propylene Demand by Derivative 1990 - 2025

160000 Demand growth 1990-2001 = 8.3% p.a.

140000 Demand growth 2001-2025 = 4.5% p.a.
120000
Thousand tons

100000
World
80000

60000

40000

20000

0
1990 1995 2000 2005 2010 2015 2020 2025

PP ACN Cumene Oxos PO Others

Main growth by PP! 36

source: ChemSystems
Proven Routes for C3= production

Steam cracker Propanedehydrogenation (PDH)

C2=:C3= = 3:1 selective C3= production
selected locations (rich NG)
37
MTP: Simplified Process Flow Diagram

Methanol optional
Fuel Gas
1.667 Mt/a = 5000 t/d internal use Ethylene
20 kt/a

DME Propylene
Pre- 474 kt/a 1)
Reactor
Product
Conditioning LPG
41 kt/a

Gasoline
MTP Reactors 185 kt/a
(2 operating + 1 regenerating)
Product
Olefin Recycle Fractionation
Water Recycle
Process Water 935 kt/a
for internal use
1) Polymer grade
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MTP Projects – gas- and coal-based

Plant production exp.

Status
location P/PP, kt/a s-u
Iran 100 BE in progress 2010

China I (coal
474 Order, Dec.05 2009
based)
China II (coal
474 Order, June. 06 2009
based)

Various prospects are not listed

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Gas-based Refinery via Methanol: Lurgis MtSynfuels®

Kero/Diesel
Hydrocarbon Recycle 6,961 t/d
Hydrocarbon Recycle

Methanol Olefin Olefin Oligo- Product Gasoline

19,200 t/d Production merisation separation 877 t/d
+ MD Hydrogenation

H2,70 t/d,
from Methanol LPG
Water synthesis
recycle 741 t/d

Process water, 10,115 t/d,

can replace raw water maximum diesel case
64,000 bpd total products
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Synfuels, Mossel Bay, RSA

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 Block Flow Diagram – Routes to Fuel & Monomer

O l i go m e r -
D i e se l p o o l
i sat i o n

Natural Gas


C o al Syngas M e t h ano l O le f in
R e si d ue P l ant P l ant P r o d u c t io n
B io m ass

P o l y-
P r o p yl e ne p r o p yl e ne
b o o st i ng P l ant

42
Conclusions

Syngas/MeOH are the key intermediate to convert any carbon

containing feedstock into value added products

Lurgi offers the whole technological chain (syngas, MeOH

and monomer/fuel)

Down-stream methanol is not a vision, it is reality!

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Thank you!

Methanol production

Conventional Outlets

Monomer Production (today)

Fuel Production (tomorrow)

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Comments?

Contact :

Dr. Thomas Wurzel

Director Gas to Chemicals
Dept. L-TG
Phone +49 69 5808 2490
Fax +49 69 5808 3032
e-mail Dr.Thomas.Wurzel@lurgi.com

Lurgi AG
Lurgiallee 5
D-60295 Frankfurt am Main
Germany
Internet: www.lurgi.com

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