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The Methanol Synthesispast and futureJohn Bøgild Hansen - Haldor Topsøe
International Methanol Conference
Taastrup – May 10, 2017
2
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
7
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
9
CO2Black Liq.
Water
WGS Sulphur
Guard
MeOH
Synthesis
AGRDME
Unit
Methanol from sustainable sourcesBioDME Black Liqour to Green DME Demo
10
DOE Project
Green Gasoline from Wood Using Carbona Gasification and Topsoe TIGAS Processes
Wood to Gasoline
11
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
12
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
13
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
14
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
16
Synergy between SOEC and fuel synthesisEffciencies electricity to MeOH = 76-79 % possible
SOEC Synthesis
CO2
H2O
SyngasProduct
Steam
17
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
19
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
20
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
21
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
23
Mass Flows in Wood to MeOH
1000 tons Wood 704 tons CO2
523 tons MeOH262 tons Oxygen
59 % LHV efficiency
24
Mass Flows in Wood + SOEC to MeOH
1000 tons Wood 782 tons Oxygen
1053 tons MeOH262 tons Oxygen
141 MW electricity 71 % LHV efficiency
25
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
26
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.