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Cost efficient Methanol Production by Autothermal Reforming Esben Sorensen, Haldor Topsoe Inc.

IHS 32nd Annual World Petrochemical Conference

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Presentation Outline

• A few words about Haldor Topsoe

• Methanol Process Optimization

• Methanol Technology Timeline

• Syngas from steam reforming (SMR)

• Syngas from 2-step reforming

• Syngas from autothermal reforming (ATR)

• Technology Development

• Economic optimization

• Risk abatement

• Economic Opportunities arising from State-of-the-Art methanol production

Fairway Methanol plant – North America´s largest

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Haldor Topsoe Company

• Established in 1940 by Dr. Haldor Topsoe. Private 100% family owned company

• Global market leader in heterogeneous catalysis with a 75 year long track record

• ~2,700 employees in 11 countries across five continents.

• HQ in Lyngby, Denmark, HT Inc. located in Houston ~ 250 employees

• Revenue about $1 billion.

Active phase Pore structure Catalyst Reactor

• Products for the Petrochemical, Refinery and Sustainables business segments

• Founded on the belief that applied fundamental research is key to build and retain a leading position in catalysis

• Up to 10% of revenue spent on R&D

Services:

• Catalysts

• Technology/licensing

• Engineering

• Hardware

• Operation assistance

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Fueling Technology and Catalyst sale through R&D and Service

Technology

Catalysts

Research and

development

Technology Licensing

Catalyst & HW sale

Client ̴ 90% catalyst resale

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Topsoe as Methanol Technology Licensor

• Leading process developer

• In the MeOH business since 1969

• Technologies for Efficient Syngas Generation

• Low S/C (down to 0.6)

• Low CAPEX

• Low Energy consumpt: <24 MMBTU/ST MeOH

• Low CO2 emission

• Compact synthesis

• Robust and cost effective methanol reactor and catalyst

• Tailor-made designs as well as standard designs available

• Integrated optimization of catalyst/reactor/process

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Methanol Process Optimization

Key specifications for syngas:

• (H2–CO2)/(CO+CO2) ratio close to 2

• High CO/CO2 ratio

• Low CH4 content

Reforming accounts for about 40% of plant CAPEX

• Minimization of S/C-ratio

• Compact design

• Favourable CO/CO2

High quality syngas gives

• Compact methanol synthesis

• Low compression costs

• Low catalyst costs

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Selection of Syngas Technology for Methanol

Module S/C CO2 CH4

Steam Reforming (SMR) Conventional tubular reforming

~3

2-3

High

Medium

Two-step reforming Combined tubular and oxygen-blown secondary reforming

~2

1.5-1.8

Medium

Low

Autothermal reforming (ATR) Stand-alone oxygen-blown reformer

1.85

0.6

Low

Low

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SMK

SMR

1st methanol plant

MK-101

Two-step reforming

Standard co prod.

3,000 MTPD plant

5000 MTPD plant

FENCE tech.

MK-151 FENCE

Flexible co prod.

ATR

MK-121

Boiling water reactor

Methanol Production from Natural gas – Timeline

1969 1986 1996 1999 2003 2009 2014 2000 1992

2,500 MTPD plant

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Methanol Production by Steam Reforming

Sulfur removal

Hydrogenator

Pre-reformer

Natural gas

Product methanol

Steam reformer

Water

Raw methanol

Raw methanol storage

Condensate

Light ends to fuel

Steam

Makeup comp.

Steam

Methanol reactor

Steam

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Methanol Production by Steam Reforming

• Process as we know it today introduced in the sixties

• Produces syngas with

• Excess H2 leading to high energy consumption

• Low CO/CO2 ratio leading to low syngas reactivity

• High methane slip leading to low reactivity and high energy consumption.

• Requires

• High S/C-ratio leading to high mass flux and high heat consumption

• Heat transfer at elevated process temperature leading to expensive reformer tubes and high heat transfer area

• Suffers from scalability issues due to sheer size considerations.

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Methanol production by Two-step Reforming

Sulfur removal

Hydrogenator

Pre-reformer

Natural gas

Product methanol

Steam reformer

Water

Raw methanol

Raw methanol storage

Condensate

Light ends to fuel

Steam

Makeup comp.

Secondary reformer

Steam

Oxygen

Methanol reactor

Steam

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Methanol Production by Two-step Reforming

• Process as we know it today introduced in the nineties

• Produces syngas with

• Stoichiometric composition leading to low energy consumption

• High CO/CO2 ratio leading to high syngas reactivity

• Low methane slip leading to higher reactivity and lower energy cons.

• Enables

• Lower S/C-ratio leading to lower mass flux and heat consumption

• Heat transfer at lower process temperature leading to less expensive reformer tubes and lower heat transfer area

• > 5000 MTPD MeOH in single line

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Hy

dro

ge

na

tio

n

Su

lfu

r re

mo

va

l

Pre

refo

rmin

g

Me

tha

no

l sy

nth

esi

s

Au

to

the

rma

l re

form

ing

Oxygen

Natural gas

Steam

Steam

Hydrogen recovery

Purge gas

Raw methanol

Makeup compressor

Recycle compressor

Steam

Methanol Production by Autothermal Reforming

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Methanol Production by Autothermal Reforming

• Advantages

• CAPEX and OPEX reductions due to elimination of steam reformer and lower throughput for same production

• More reactive syngas leading to lower cost of methanol synthesis

• The ATR enables

• Operation at S/C-ratio = 0.6 leading to smaller sizes and higher CO/CO2 ratio

• Increased reforming temperature leading to lower methane slip

• Much simpler lay-out - Replacing steam reformer with fired heater

• Stoichiometric syngas

• Obtained by means of HRU

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Technology Comparison – Typical USGC Natural gas

5,000 MTPD MeOH plant Two-step reforming ATR

Energy consumption, including oxygen

100 99

ISBL cost including ASU 100 91

Catalyst cost 100 95

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Economy of scale

• Two-step reforming

• S/C ratio 1.5 - 1.8

• O2-demand: 0.48 MT/MT MeOH

• Steam Reformer

• ATR

• S/C ratio 0.6

• O2-demand: 0.62 MT/MT MeOH

• Fired Heater and Hydrogen Recovery Unit

• Economy of scale

• Favors ATR

• Break-even depends on feed gas composition

Co

st

Capacity

Tubular reformer

Oxygen plant

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ATR – Industrial experience

• Oryx GTL, Qatar

• The largest ATRs in the world

• 2 x 180,000 Nm3/hr natural gas feed

• S/C ratio of 0.6

• 34,000 BPD diesel and naphtha

• Equivalent to 2 x 5,900 MTPD MeOH

• Start-up in 2006

• Topsoe supplied syngas section

• License

• Proprietary hardware

• Catalyst

• Engineering services

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Oxygen

Natural gas and steam

CTS burner

Combustion chamber

Syngas

Pressure shell

Refractory

Catalyst

Target tiles

Catalyst bed support

Topsoe ATR Safe and innovative solutions

• Innovative solutions improve reliability • Burner technology

• Refractory linings

• Catalyst bed solution

• Safe operation • More than 70 years at low S/C ratio

• > 99% operation availability for ATR unit • Between major turnaround periods

• Excluding trips caused by events outside the syngas unit

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Hydrogen Recovery Units – Industrial experience

• Two Options for HRU:

• PSA units

• Membrane Separation processes

• PSA units:

• Vast experience base from hydrogen plants at lower pressure

• Available at relevant pressure last 10+ years

• Membrane units:

• Industrial commodity since 2000

• Application to methanol synthesis:

• Haldor Topsoe has running references with both types of HRUs

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ATR based MeOH plant – State of the Art Consumption figures

5,400 MTPD MeOH plant MM BTU/MT MeOH (LHV)

Energy consumption, NG feed & fuel 27.3

Electric power 0.2

Steam export (1.3)

Net consumption 26.3

O2 consumption 0.62 MT/MT MeOH

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Economic Opportunities – ATR based MeOH plant

5,000 MTPD MeOH plant Cost USD MM

(incl. ASU)

Methanol Plant (incl. owners cost) 536

OSBL costs 327

Total project cost incl. financial exp. 1,079

Annual CAPEX (70/30 Debt/Equity)

91

Annual OPEX (3.5 $/MMBTU)

265

Return on investment – 1st year (280 $/ton MeOH)

42%

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ATR based MeOH plant – Advantage of Oxygen supply Opportunities

5,000 MTPD MeOH plant Cost USD MM

Oxygen import Cost USD MM

Incl. ASU

Methanol Plant (incl. owners cost) 416 536

OSBL costs 254 327

Total project cost incl. financial exp.

837 1,079

Annual CAPEX (70/30 Debt/Equity)

70 91

Annual OPEX (3.5 $/MMBTU)

280 265

Return on investment – 1st year (280 $/ton MeOH)

56% 42%

Details can be obtained by mailing to els@topsoe.com

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Summary

• Haldor Topsoe is a leading methanol technology licensor and catalyst supplier

• Methanol production by ATR is State-of-the-Art

• ATR operating at S/C ratio 0.6 is an industrial reality

• Savings both on CAPEX and OPEX compared to previous generations of methanol processes

• Methanol production by ATR gives very attractive return on investment

• US Golf Coast brings special opportunities due to availability of OTF oxygen supply

+ =

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Our Values

Business: We go the extra mile to create lasting value for our customers.

Science: Our passion for science and innovation strengthens our business.

People: Topsoe is a great place to work and to have worked.

Society: We create sustainable solutions that make a difference to the world of today – and tomorrow.