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 Todays methanol industry Towards larger capacities a joint effort of R&D, catalyst development and plant engineering Monomer and fuel from Methanol Conclusions

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
 

How will the future look like?

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

754 hits

Syngas & MeOH the flexible dream team

Coal Natural Gas BioMass Tar Sands etc.

Chemicals Propylene DME Fuels

Syngas

Methanol

Chemical Methanol Market

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

development up down up up

annual increase pre-dominant feedstock: close the gap in low cost methanol supply: selection of syngas technology is key to economic methanol production

3 % i. e. 1 MM tpa natural gas MegaPlants (> 1 million tpy) 60 65 % of ISBL cost

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Ways to produce Syngas

Heavy Naphtha LPG Refinery Off-gases Residue Prereforming
Gasification

Coal

Natural Gas Prereforming MPG Secondary Reforming Autotherm. Reforming

Tubular Reforming Tubular Reforming

MPG H2S Rectisol

Tubular Reforming

H2S Rectisol

CO Shift Conversion

CO2 Removal Cold Box PSA

PSA

H2

H2

CO

Synthesis Gas

H2/CO Ratios for Syngas Generation

S MR

C MR

A T R

MPG
1
F e e d N atu ral G as

H2/CO ratio

CMR= Co m b i n e d Me t h a n e Re f o r m i n g
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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 W orld largest sin gle t rain sy n gas un it ( A T LA S ) orld largest m ult ip le t rain sy n gas un it ( M p erat ure for a st eam reform osselb ai) er ( B P

S ic h uan p lan t )

H igh est out let t em

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 P ilot p lan t t o t est 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

ore sev ere op erat in g c on d it ion s

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Syngas Benchmarks for MeOH Parameter

Stoechiometric number, SN CO/CO2 ratio Methane slip, % (dry) Steam reformer duty, GJ/hr Syngas flow at compressor suction, m3eff. / hr

Steam Reforming 2.95 2.3 3.28 1740 43713

Autothermal Reforming 2.05 2.5 1.76

-

Combined Reforming 2.05 2.8 2.10 460 19433

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20240

Syngas Benchmarks for MeOH

Parameter
Capacity, MTPD
Natural gas consumption (MMBTU/ton MeOH)

Conventional Technology 2500 30 100 100 100

MegaMethanol Technology 5000 28.5 130 97 79

Investment1), % Operating cost, % Production cost, %

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 -Al2O3 Nickel catalyst high thermal stability multilayer refractory lining thermal protection

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Development steps towards MegaSyn

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Atlas Methanol - 5000 mt/d, commissioned 2004

Milestones in ATR History

1922 1928 1954 1979 2004

Autothermal Reforming (recuperative mode) Lurgi introduces oxygen-based gas production (coal gasification) First Lurgi ATR (Towngas production) First application of combined reforming 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

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PetroSA, Mosselbay, 1993

Feedstock: Natural Gas Product: Fischer-Tropsch Syngas Capacity: 252 MMSCFD per train
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ATLAS, Trinidad, 2004

Feedstock: Natural gas Product: Methanol Syngas Capacity: 420 MMSCFD

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Base of Fluid Dynamical Simulation

Thermo-chemical Model

Reactor/ Burner Geometry

Navier-Stokes Equations

Velocity temperature 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 Temperature C 270 265 260 255 250 245 240 0 0,2 0,4 0,6 0,8 1
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Reaction Cooling Water

Catalyst Height

Development of Synthesis Loop Steam Raising Reactors

Interchanger

Steam Drum

Reactors

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Development of Synthesis Loop 2. Two-Step Methanol Synthesis

Recycle Compressor Gas-cooled Reactor Steam Raising Reactor MP-Steam

Compressed Synthesis Gas

Purge Gas

Crude Methanol

Boiler Feed Water

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Development of Synthesis Loop Lurgis 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 200 150 100 50 0 0 0,2 0,4 0,6 0,8 1 Catalyst Height
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Reaction Cooling Gas

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

Gas Cooled Reactor
g

Steam Raising Reactor

g g g g g g

Simple and Exact Reaction Control Quasi Isothermal Operation High Methanol Yield High Energy Efficiency (80 %) Kinetically controlled

Operation at the Optimum Reaction Route High Equilibrium Driving Force High Conversion Rate


g Heat of Reaction converted to MP steam g g

Elimination of Reactor Feed Preheater Elimination of Catalyst Poisoning 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 synthesis
Syngas Flow Recycle Flow Synthesis Loop Pressure Methanol Content Reactor Outlet m3N/t MeOH m3N/t MeOH bar mol% 2580 8500 80 7

Two step synthesis

2550 5100 75 11

The implementation of the MegaMethanol technology represents a unique joint effort comprising technology development and catalyst research (Sd-Chemie)
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Propylene Demand by Derivative 1990 - 2025

160000 140000 Thousand tons 120000 100000 80000 60000 40000 20000 0 1990 PP

Demand growth 1990-2001 = 8.3% p.a. Demand growth 2001-2025 = 4.5% p.a.

World

1995 ACN

2000

2005

2010 Oxos

2015

2020 PO

2025 Others
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Cumene

Main growth by PP!

source: ChemSystems

Proven Routes for C3= production

Steam cracker C2=:C3= = 3:1

Propanedehydrogenation (PDH) selective C3= production selected locations (rich NG)

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MTP: Simplified Process Flow Diagram

Methanol 1.667 Mt/a = 5000 t/d

Fuel Gas internal use

Ethylene
20 kt/a

optional

DME PreReactor

Propylene 474 kt/a 1)

Product Conditioning LPG 41 kt/a

(2 operating + 1 regenerating)

MTP Reactors

Gasoline 185 kt/a

Olefin Recycle Water Recycle 1) Polymer grade

Product Fractionation Process Water 935 kt/a

for internal use
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MTP Projects gas- and coal-based

Plant location
Iran China I (coal based) China II (coal based)

production P/PP, kt/a

100 474 474

Status
BE in progress Order, Dec.05 Order, June. 06

exp. s-u
2010 2009 2009

Various prospects are not listed

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Gas-based Refinery via Methanol: Lurgis MtSynfuels

Hydrocarbon Recycle Hydrocarbon Recycle

Kero/Diesel
6,961 t/d

Methanol
19,200 t/d

Olefin Production

Olefin Oligomerisation

+ MD Hydrogenation

Product separation

Gasoline
877 t/d

Water recycle Process water, 10,115 t/d, can replace raw water

H2,70 t/d, from Methanol synthesis

LPG

741 t/d

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 i sat i o n
Natural Gas C o al R e si d ue B io m ass

D i e se l p o o l

Syngas P l ant

e t h ano l P l ant

O le f in P r o d u c t io n P r o p yl e ne b o o st i ng P o l yp r o p yl e ne P l ant

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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 Fax e-mail +49 69 5808 2490 +49 69 5808 3032 Dr.Thomas.Wurzel@lurgi.com Lurgi AG Lurgiallee 5 D-60295 Frankfurt am Main Germany Internet: www.lurgi.com
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