Fra el og bio til grøn gas

Fra el og bio til grøn gas
John Bøgild Hansen, Haldor Topsøe
Gastekniske Dage, Billund, Maj 13, 2015
Topsøe TREMP™ Methanation
proces
SNG fundamentals and references
 Methanation to SNG CO + 3H2 ↔ CH4 + H2O
CO2 + 4H2 ↔ CH4 + 2H2O
(+206 kJ/mol)
(+165 kJ/mol)
 +200 references in steam reforming, using Nickel-based
catalysts (front-end ammonia, hydrogen, methanol, SNG
from coal and biomass)
 More than 50 years of Topsoe experience
 Sintering stability
 Methanation activity
 Carbon formation (whisker, gum)
SNG from naphtha (1966)
Energy transportation system
Chemical recuperation of nuclear energy
HTR
Eva
Adam
Catalyst experience
ADAM 1
ADAM 2
Methanation essentials
 CO + 3H2 = CH4 + H2O
 CO2 + 4H2 = CH4 + 2H2O
20% Heat
100%
Syngas
from
SOEC
Methane
Heat recovery is the key to an efficient plant!
80% CH4
SNG Technology
Working on the Methanation equilibrium curve
1200
1100
1000
900
800
T, °C
700
600
500
400
300
200
Removal of water
100
to shift curve
0
0
10
20
30
40
50
% CH4, dry
60
70
80
90
100
TREMP flow scheme
Sulphur
guard
Recycle
methanator
2nd stage
methanator
3rd stage
methanator
Feed
P = 30 kg/cm2g
SNG
T °C
250
325/650
494
342
35
CH4 vol %
(DRY)
12
57
80
94
94
ADAM1 – Temperature Profiles
R101 (MCR-2X)
Temperature °C
700
600
R102 (MCR-2X)
500
400
R103 (MCR-4)
300
200
O/C = 1
H/C = 6
P = 27 bar
50
0
100 Z. cm
Temperature profiles from adam 1
High temperature methanation catalyst (MCR)
 Slight modifications have given an even more stable
catalyst
Temperature (ºC)
700
600
500
1h
400
358 h
1028 h
300
0
50
Distance from inlet (cm)
~1980
2010
100
World largest SNG plant started 2013
Quinghua, China – 1.4 billion Nm3 per year
 Topsoe did SNG design, license and catalyst supply
Present Topsoe projects for fuel solutions based
on coal, COG and biomass
 Bio-based plants
 Wood based plant to make gasoline (USA)
 Wood based plant to make SNG (Sweden)
 Black liquor to make MeOH/DME (Sweden)
 COG based plants
 6 large scale plants to make SNG/LNG for PetroChina and CNOOC
 Technology for gasoline production
 Coal based plants
 4 large scale plants to make SNG for POSCO, Korea; Qinghua,
Xinjiang; Huineng, Inner Mongolia; and CPI, Xinjiang, China
 Technology for gasoline production
Fuel Cell and Electrolyser
SOFC
H2O
H2
SOEC
H2
H2O
H2 + O2- → H2O + 2e-
H2O + 2e- → H2 + O2-
O2-
O2-
½O2 + 2e- → O2-
O2- → 2e- +½O2
½O2
H2 + CO + O2
½O2
SOF
C
H2O + CO2 + electric energy (∆G) + heat (T∆S)
SOEC
Electrolysis
Power
Steam
CO2
CO
H2
CO2
Syngas
Hydrogen
SNG
Methanol
DME
Gasoline
Diesel
Biogas to SNG via SOEC and methanation
of the CO2 in the biogas
SOEC
Oxygen
Biogas
Steam
Methanator
Water
SNG
Condensate
Exergy Flows in CO2 case
Synergy between SOEC and fuel synthesis
Product
CO2
SOEC
Synthesis
Syn
Gas
H2O
Steam
New EUDP project
40 kW SOEC and 10 Nm3/h methane
Participants:
Haldor Topsøe A/S
Aarhus University
HMN Naturgas
Naturgas Fyn
EnergiMidt
Xergi
DGC
PlanEnergi
Ea Energianalyse
Cemtec
Coordinator:
Duration:
June 2013 July 2016
Project sum:
5.3 mio €
Location:
Foulum
Key numbers
Denmark (2008)
 Final energy consumption: 673 PJ
 Biogas potential: 40 PJ
 If upgraded by SOEC: 67 PJ ~ 10 %
 NG used for power plants: 73 PJ
 NG used in household, industry and service: 76 PJ
 Saved CO2 ~ 1 MT/capita
Bio-SNG layout
BioSNG
Air
Air
Separation
Unit
CO2
Drying
O2
Tar
reforming
Biomass
CO2
Removal
Gasification
H2O
Tar removal
COS
hydrolysis
Acid
Gas
Removal
CO2/ H2S
Water
Gas Shift
Synthesis
Green Synthetic Natural Gas
- GoBiGas, Gothenburg
 A 20 MW (SNG – 2,200 Nm3/h)
commercial plant in Gothenburg
(Sweden) with Topsoe SNG technology
 If coupled with SOEC production of
SNG coulbe increased by 180 % !
CO2 Electrofuel Project
Sponsored by NER
Wood gasification to Methanol
CO2 to Methanol
Landfill to SNG
Wood to Methanol
Biogas to SNG
Wood gasification
to SNG
Electrolytic biogas upgrading model for
economic assessment
Biogas unit
Power
grid
Power
Biogas
Steam
Steam
SOEC
H2
H2
H2
Storage
Methanator
SNG
NG
grid
Water
Oxygen
Economics of Icelandic Landfill gas Upgrading
Economics of Biogas upgrading, Southern Sweden
Challenges no 2:
Biogas plants are small
 Biggest modern SNG plant
started up is in China:
Xinjiang, Qinghua
 Largest single train SNG plant ever: 1,4 billion Nm3/year = 50 PJ/year
 One biomass gasification plant @ 200 MW wood
= 4 PJ/year
 One biogas upgrading plant @ 5 million Nm3 biogas
= 0,06 PJ/year
We need economy of numbers not scale !
Challenge no 1:
Fluctuating electricity prices
Power production
•SOFC?
Electrolysis
•SOEC
Conclusions
 Biogas can be upgraded electrochemically by SOEC to
pipeline quality
 Consumption of electricity 13 – 14 kWh per Nm3
methane
 Complete sulphur clean up has been proven sucessfully
 Methanation is proven technology
 Economic analysis has shown that upgrading by SOEC
can compete with traditional upgrade by CO2 removal
 10 % of Denmarks energy consumption could be
achieved and 1 MT CO2 per capita per year saved
Comparison of steam and co-electrolysis
for a 7,500,000 Nm3/year biogas plant
Configuration
Unit
Investment
Million €
4.44
4.30
Value of SNG
€/GJ
18.8
24.0
19.8
Hours of
operation
Hours
7480
7735
8300
Average
electricity price
€/MWh
46.6
47.0
33.0
Net present
value
Million €
4.83
4.56
Assumptions:
Subsidy:
Denmark
6.6
€/GJ
Sweden
Iceland
IRMA
Load and T-max
Energinet.dk’s vision for fossil fuel free
Denmark in 2050 – The Wind Scenario
El- Transmission
Low priced
Peak Shave:
Gas Turbine
SOFC
SOEC
Electrolysis
District Heating
Heat
O2
DH
Biomass
High priced
Gasifier/
Digester
Cleaning
DH
Gas
System
Storage
Catalysis:
MeOH, DME
Gasoline, SNG
Green Synfuels
District Heating
District Heating
Air
Capture
Compress
Gas Transmission
Upgrade
To
Methane
The CO2 Electrofuel Project
CHEMREC
Energy to Succeed
Is CO2 electrofuels a viable and competitive technology for the Nordic countries?
Bulk methanation
GCC
MCR
MCR
34
Trim methanation
Domestic renewable resources to reach 100
per cent renewable energy by 2050
Danish Commission on Climate Change Policy, 2010
1400
Used today (2008)
1200
Potential
Wind scenario
2050 (recommendation)
PJ per year
1000
Gross energy consumption 2008
800
Gross energy consumption 2050
600
Energinet.dk
analysed high
wind scenario
400
200
0
Wind
Source:
2012-04-23
Sun
Wave
Fluctuating
power production
Renewable gases as a flexibility provider for the power grid
Heat
Biomass and
(sun, geo. and waste (incl.
heat pump)
slurry)
36
Poul Sabatier
CO + 3H2 = CH4 + H2O
Methanation approaches
900
1
ADAM 1: C 3-4-5; 3 reactors, recycle ratio 1.1 Nm3/Nm3;
reference case
A 1-2-3-4-5: 5 reactors, no recycle
B 3-4-5; 3 reactors. recycle ratio 2.7 Nm3/Nm3
800
Temperature, °C
2
700
3
A1 - Make-up gas
Equilibrium curve
600
4
500
A1
400
F
5
300
C
* O/C = 0.94;
H/C = 5.7;
P = 27 bar
200
0
50
CH4, dry vol %
100
TREMP, Typical Process
Flow Diagram
Feed
R2
R1
R3
R4
Superheater
HP
boiler
HP
boiler
Cooling
Train
SNG
Water
SNG Technology
Typical specification for substitute natural gas
(SNG)
Mole%
CH4
94 - 98
CO2
0.2 – 3
H2
0.1 – 2
CO
<100 ppm
N2 + Ar
HHV, KJ/Nm3
1-3
37,000 - 40,000
Results from Jülich / Wesseling demonstation
 Reactor designs
– Isothermal reactors
 Salt
 Boiling water
– Adiabatic reactors
– Shell cooled
– Gas cooled reactors
 Catalyst
– MCR-2
 Demonstrated up to 800 deg. C
 More shapes
– MCR-4
CAPEX estimate
 Total capacity:
1,400,000,000 Nm3/a
 Total price:
approximately 1.5 billion EUR
(install cost, all inclusive)
– Syngas generation etc.
65%
– Rectisol
15%
– TREMP
10%
– Sour shift
5%
– SRU
5%
– Total
100%
Summary of TREMP benefits
 Proven technology:
– More than 55000 demonstration hours
– Currently largest running reference (Qinghua)
 High quality: In-process compensation for feed-gas module
variation
– Combining high performance with robust process
 No continuous emissions to the atmosphere
 Provides both catalyst and technology solutions
 Clean process condensate (can be used as make-up for the
steam system)
Methane content as function of pressure
100
CO
Dry methane %
CO2
95
90
85
0
5
10
15
20
25
Pressure, kg/cm2 g
30
35
40
45
Topsoe SNG plants
Client
Location
Capacity Nm3/yr
Qinghua
China
Year awarded
Start-up
1.4 billion
2009
2013
Gobigas (Bio-based) Gothenburg, Sweden
19.4 million
2010
2014
Petrochina (COG)
Wuhai, Inner Mongolia, China
2 x 450 million
2011
2013
Huineng
Inner Mongolia, China
400 million
2011
2014
CNOOC (COG)
Shandong, China
160 million
2011
2013
CPI
Yili, Xinjiang, China
2 x 1 billion
2011
2015
POSCO
South Korea
700 million
2010
2014
Guizhou
Guizhou, China
290 million
2013
2015
SANJU (COG)
Inner mongolia
470 million
2014
2014
SOEC more efficient than present Electrolysers
Internal waste heat used to split water
4.0
Energy needed to evaporate water
3.5
kWh per Nm3 H2
3.0
Waste heat which can be utilised to split water
2.5
2.0
1.5
Minimum Electricity Input
1.0
0.5
0.0
0
100
200
300
400
500
Deg C.
600
700
800
900
1000
We have been committed to catalytic
process technology for more than 70 years
 Founded in 1940 by Dr. Haldor
Topsøe
 Revenue: 700 million Euros
 2400 employees
 Headquarters in Denmark
 Catalyst manufacture in
Denmark and the USA
Business case for biogas upgrading
Livestock, Windturbine capacity and NG consumption per capita
2,50
2,00
1,50
Pigs
Cattle
Wind,kW
NG MTOe
1,00
0,50
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