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The Methanol Synthesispast and futureJohn Bøgild Hansen - Haldor Topsøe

International Methanol Conference

Taastrup – May 10, 2017

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We have been committed to catalytic process technology for more than 70 years

• Founded in 1940 by Dr. Haldor Topsøe

• Revenue: 700 million Euros

• 2700 employees

• Headquarters in Denmark

• Catalyst manufacture in Denmark, China and the USA

3

Topsøe methanol technology and catalyst milestones

69’ 86’ 00’ 09’92’ 96’ 03’

1st methanolplant

SMK

CMD revampconcept

MK-101

MK-121 MK-151FENCE™

World scaleplant

Two stepreforming

2 * 5000 MTPD scaleplant

15’

4

Topsoe methanol plantsSince 2000

Number of plants: 40

Accumulated capacity, MTPD: 97,075

Number of catalyst charges: 168

2

17

12

2

7

5

Methanol market share

HTAS

28%

Davy

26%

Lurgi

15%

Casale

13%

Chinese Lic.

4%

Others

14%

Awarded capacity 2003-2014

6

• Optimising sintering barriers

• Cu crystals separated by picket fence of metal oxides

• The FENCE™ technology inhibits sintering

CuZnO Al2O3

FENCE™ technology

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Increased loop efficiency

– Production gain

– Increased carbon efficiency

– Lower energy consumption

Longer catalyst lifetime

– Less replacements

– Increased plant availability

Industrial experience

Days on Stream

Ca

taly

st a

ctivity

MK-151 FENCE™

MK-121

MK-101

20%

20%

MK-151 FENCE™

MK-121

MK-101

Statoil, Norway, 2500 MTPD

28.8 GJ/MT => 69 % efficiencyIndustrial benefits

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Reformers for Methanol Plant utilising CO2

¾CH4 + ½H2O + ¼CO2 = CH3OH

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CO2Black Liq.

Water

WGS Sulphur

Guard

MeOH

Synthesis

AGRDME

Unit

Methanol from sustainable sourcesBioDME Black Liqour to Green DME Demo

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DOE Project

Green Gasoline from Wood Using Carbona Gasification and Topsoe TIGAS Processes

Wood to Gasoline

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The Active Site of Syngas Catalyst

Cu(111),d=0.21nm

Cu(200),d=0.18nm

ZnO(011),d=0.25nm

ZnO(012),d=0.19nm

Cu(111)

Cu(111)

H2 H2/H2O

1.5mbar, 220oC 1.5mbar, H2/H2O=3/1, 220oC

Cu is metallic when catalyzing• WGS • MeOH synthesis • MeOHreforming

Catalyst dynamic• Number of active

sites depends on conditions

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Conversion of methanol as function ofCO2 content in stoichiometric gas

0

10

20

30

40

50

60

70

80

90

100

0 5 10 15 20 25 30

Percent CO2 in

Ca

rbo

n c

on

ve

rsio

n %

J.B. Hansen Data

Condensing methanol

K.Klier Data

Lab data 225 C

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Fuel Cell and Electrolyser

½O2

H2 H2O

½O2

H2O + 2e- → H2 + O2-

O2-

O2- → 2e- +½O2

H2 + O2- → H2O + 2e-

O2-

½O2 + 2e- → O2-

SOFC SOEC

H2H2O

H2 + CO + O2 H2O + CO2 + electric energy (∆G) + heat (T∆S)SOFC

SOEC

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MethanolFrom CO2 and Steam

Water

SOECOxygen

CO2

Me

tha

no

l sy

nth

esi

s

Se

pa

rato

r

Methanol

Purge

Recycle

15

Reactor volume and byproducts as functionof CO2 converted in SOEC

0

300

600

900

1200

0

100

200

300

400

500

600

700

0 20 40 60 80 100

Byp

rod

ucts

Rela

tive %

Reacto

r V

olu

me R

ela

tive %

Percent CO2 through SOEC

Byproducts

Reactor Volume

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Synergy between SOEC and fuel synthesisEffciencies electricity to MeOH = 76-79 % possible

SOEC Synthesis

CO2

H2O

SyngasProduct

Steam

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EUDP project50 kW SOEC and 10 Nm3/h methane

Participants:

Haldor Topsøe A/S

Aarhus University

HMN Naturgas

Naturgas Fyn

EnergiMidt

Xergi

DGC

PlanEnergi

Ea Energianalyse

Coordinator:

Duration:

June 2013 -

September

2017

Project sum:

5.3 mio €

Location:

Foulum

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Methanation and SOEC at Foulum

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Productionvs hours on stream. 3.1 kWh/Nm3 H2

700

720

740

760

780

800

820

0%

20%

40%

60%

80%

100%

120%

0 200 400 600 800 1000 1200 1400

Op

era

tin

g T

em

p C

Pe

rce

nt

of

De

sig

n p

rod

ucti

on

Hours on Electrolysis

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Results from Foulum Methanator

200

250

300

350

400

450

500

550

600

650

700

0 0,5 1 1,5 2 2,5 3

Deg

. Ce

lciu

s

Meters from catalyst inlet

Temperature profile in Methanator

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Average gas compositions

Position CH4 CO2 N2 H2

Biogas 56 43 1 0

Exit 1st

stage94.58 0.27 0.91 4.23

Product gas

97.69 0.00 0.95 1.36

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GreenSynFuel Project

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Mass Flows in Wood to MeOH

1000 tons Wood 704 tons CO2

523 tons MeOH262 tons Oxygen

59 % LHV efficiency

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Mass Flows in Wood + SOEC to MeOH

1000 tons Wood 782 tons Oxygen

1053 tons MeOH262 tons Oxygen

141 MW electricity 71 % LHV efficiency

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EffcienciesStand alone wood gasifier and gasifier plus SOEC

LHV Efficiency %

Wood Gasifieralone

Wood gasifierPlus SOEC

Methanol 59.2 70.8

District Heat 22.6 10.8

Total 81.8 81.6

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Conclusions

• Haldor Topsøe is a major player within the methanol industry

• CO2 is already today used to enhance methanol production based on natural gas steam reforming

• Very efficient methanol plants based on power, steam and CO2 is possiblevia SOEC

• Co-electrolysis offers the opportunity to reduce methanol synthesiscatalyst volumes by a factor around 5

• Coupling SOEC with biomass gasification can double the biomass potential by converting excess carbon.

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