Michael Specht, Ulrich Zuberbühler, Andreas Bandi Centre for Solar Energy and Hydrogen Research (ZSW), Stuttgart Experimental Data on Renewable Methanol/Methane Generation from Atmospheric CO 2 in Pilot Plants Brainstorming Workshop Sustainable methanol: An alternative green fuel for the future 22./23.11.2011, IASS, Potsdam
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Michael Specht, Ulrich Zuberbühler, Andreas Bandi
Centre for Solar Energy and Hydrogen Research (ZSW), Stuttgart
Experimental Data onRenewable Methanol/Methane Generation
from Atmospheric CO2 in Pilot Plants
Brainstorming WorkshopSustainable
methanol:
An alternative green
fuel
for
the
future22./23.11.2011, IASS, Potsdam
Centre for Solar Energy and Hydrogen Research (ZSW): New Energy Technologies
• Applied Research & Development• Close Cooperation with Industry and Universities•
25 Million €
Turnover, 200 Employees
• Photovoltaic –
Thin Film Technologies (CIS) & Application Systems• Renewable Fuels and Processes• Fuel Cells –
Technology, Systems, Test Centre
• Batteries & Super Capacitors –
Materials, Systems, Qualification• Systems Analysis and Policy Consulting
Stuttgart Widderstall Ulm
Strategy Change at ZSW: Renewable Carbon-based Fuels
C-Resource: “CO2
from Air” “CO2 from Biogas”
Fuel: MeOH SNG
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps
Thermodynamic Efficiency Calculations for the Conversion of Syngas to Synfuels
SYNGAS CO / H2
SYNGAS CO2 / H2
[ ]molkJ
H298Δ
Syngas
298LHV
H1 Δ−=η
[ ]molkJH298Δ
Syngas
298LHV
H1 Δ−=η
OHCH3 -90,625 0,882 -49,943 0,931
33 CHOCH -204,932 0,866 -121,682 0,916
4CH -206,158 0,796 -165,475 0,829
125 HC -802,865 0,803 -602,450 0,844
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps
Chemical Reactions in Absorber / Stripper / Electrodialysis (ED) Unit
Absorber:2 KOH + CO2
K2
CO3 + H2
O
Electrodialysis Unit:K2
SO4
+ H2
O KHSO4
+ KOH
Stripper:
K2
CO3
+ 2 KHSO4
2 K2
SO4
+ CO2 + H2
O
Regeneration of Scrubbing Liquid and Acidic Solution: Bipolar Membrane Electrodialysis of Na2 SO4 Solution
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps
Methanol Synthesis from H2 /CO2 : Reaction Conditions / Results
CO + 2 H2 CH3 OH
Δ
H = - 92 kJ / mol
CO2 + 3 H2 CH3 OH + H2 O
Δ
H = - 50 kJ / mol
Reaction Conditions:
250 -
280°C
50 -
100 bar
Cu / ZnO-based
Catalyst
Results:
SV: 8000 lsyngas
lcat-1h-1
0.7 kgMeOH
lcat-1h-1
CO Formation via Retro Shift Reaction
Methanol Synthesis from H2 /CO2 : Energetic Efficiency (Power-to-Methanol)
Energetic Efficiency calculated from ED results (LHVMeOH /ElectricityInput ):
Atmospheric CO2
: < 46 %
Flue Gas CO2
: < 48 %
“free”
CO2
: < 61 %
Renewable Methanol for Road Transport produced from H2 and Atmospheric CO2 at ZSW in 1996
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps
Power-to-Gas - Concept: Basic Layout of the Demonstration Plant in 2009
Abluft
Hydrogen Generator
2-BankKonsole
PKW
CO2-Puffer
Gastrocknung
2-Bank-Speicher
CH4-Puffer
CO2-Produktion
Kraftstoffsynthese
Di-Patrone
Trinkwasser
FIC
PIC
CO2-Absorber
Elektrodialyse CO2-Bereitstellung
H2-ErzeugungCH4-Synthese
FIC
Betankung
PIC
CO2 -Absorber
F
NaOH
Na2CO3
Coupling of Absorber / Electrodialysis Unit for Continuous CO2 -Production
K A K K
+ —
Na+
OH- H+
Na+
H2O2
CO2 Container (left) / SNG Container (right)
Absorber Packing
Design Data ofAbsorber Column:
Height: 2 x 1.05 m
Diameter: 1.2 m
CO2
Production: 40 molCO2
/h
Air Throughput: 3600 m3/h
Absorption liquid: 800 l
Absorption liquid flow:5 -
10 m3/h
Electrodialysis
Electrodialysis
stack
with
80 cells(bipolar / cation
exchange
membrans)
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps
Caustic Air Scrubber/Electrodialyisis: Experimental Data, Design Data, Optimization
Measurement2010-08-19
DesignData Optimization Remarks
CO2 abs.mol/h 35.30*) 12:10-12:30 single absorber
kW kWh/m³CO2 kWh/m³CO2 kWh/m³CO2 Standard Conditions 0°C,1013mbar
ED ges. 7.00 8.85 4.56 7.32
ED Stack 5.00 6.32 3.93 6.32 improvement with 3 chamber ED ?
∑
Pumps 2.00 2.53 0.63 1.00 lower Stack pressure
Absorber ges. 4.30 5.43 1.67 2.00
Air fan 1.30 1.64 1.04 1.00 1 absorber with reduced pressure drop
∑
Pumps 3.00 3.79 0.63 1.00
Humidifier 0.40 0.51 0.50 no improvement
Abs. 3.0.0 1.30 1.64 0.50 Distribution channel instead spraying
Abs. 4.0.0 1.30 1.64
Abs. & ED 11.30 14.28 6.23 9.32 35% Optimization Potential
CO2
Container 13.60 17.19 incl. auxiliaries
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps
All components of the system “CO2 from air” were tested in two pilot plants
Realised technology 1995: Batch operation
Realised technology 2009: Continuous operation
Worldwide first demonstration plants for CO2 generation from atmosphere (?)
From technical point of view C-based fuels can be generated from atmospheric CO2
Energetic efficiency MeOH from air-CO2: up to 46 %
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps
Path 1: (Digestive) Biomass SNGPressure Swing Adsorption (PSA) Gas Upgrading
Biogas
Vacuum pump
Off-gas(CO2)
Flushing gas
SNG
Water separator
Compressor
Des
ulph
uris
atio
n
Ads
orbe
r uni
t
Path 2: (Woody) Biomass SNG“BtG” Biomass-to-Gas
CO, H2 , CO2 , CH4
Gasification
Biomass
Producer Gas
SNG(CH1.52
O0.65
)
(Synthesis Gas)
(Gas conditioning,stoichiometry
adjustment)
1st Step 2nd Step
Synthesis
Path 3: CO2 + H2 (via Electrolysis) SNGPower-to-Gas (P2G)
Path 2 and 3: Methanation of CO / CO2
Methanation:
3 H2
+ CO CH4
+ H2
O ΔHR0
= -206,4 kJ/mol
4 H2 + CO2 CH4
+ 2 H2
O ΔHR0
= -164,9 kJ/mol
Shift- Reaction:
H2
O + CO H2
+ CO2
ΔHR0
= -41,5 kJ/mol
CO / CO2 Methanation: Development Status
Methane synthesis from CO/H2-based Syngas is a state-of-the-art technology
Methane synthesis from CO2/H2-based Syngas is not a state-of-the-art technology
Source Dakota Gasification Company: Coal to Electricity / SNG / CO2
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps
CCPP: Combined Cycle Power Plant; µ-CHP: micro Combined Heat and Power Plant
Power-to-Gas (P2G) - Concept: Interconnection with Mobility
EV:
Electric Vehicle
BEV: Battery Electric Vehicle
FCEV: Fuel Cell Electric Vehicle
CNG-V: Compressed Natural Gas Vehicle
Plug-In HEV: Plug-In Hybrid Electric Vehicle
(especial: Plug-In Electric Drive Motor Vehicles / Range-Extended Electric Vehicle)
CCPP Combined
Cycle
power plant
B-CHP Block-type combined heat and power station
Solar
WindCCPP / B-CHP
CO2
buffer
Electricitygrid
Gas distribution system
Electrolysis
/
H2
bufferMethanation
H2
CO2
CH4
POWER GENERATION
ELECTRICITY STORAGE
CO2
Gas
underground
storage
Electricity H2 SNG
BEV FCEV CNG-V
Mobility
H2
CO2
Plug-In HEV Plug-In HEV
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps
Schematic Diagram of a P2G - Plant for IPSEpro Process Simulation (Feed: CO2 /H2 and Biogas/H2 )
SettingsEnergy demand electrolysis:
4 kWhel
/mN3H2
System pressure:
7 barabsGrid pressure:
16 barabs
Energy Flow of a P2G - Plant
Case
1: “CO2
/H2
-to-SNG"Case
2: "Biogas/H2
-to-SNG“
(50 / 50 [Vol.%CH4
/ Vol.%CO2
] in biogas)Case
3: "Biogas/H2
-to-SNG“
(70 / 30 [Vol.%CH4
/ Vol.%CO2
] in biogas)
Influence of Electrolysis Efficiency on P2G System Efficiency (CO2 /H2 -to-SNG)
40
45
50
55
60
65
70
3,5 3,7 3,9 4,1 4,3 4,5 4,7 4,9 5,1
Electrolysis power requirement [kWhel
/mN3H2
]
Sys
tem
effi
cien
cy [%
]
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps
Environmental Benefits: Emissions Reduction through CNG-Vehicles
-80% -80%
-20%
-40%
-10%
-60%
-90%
-10%
-80%
CO NMHC GHG OZONE CO NMHC NOx GHG OZONE
in relation to gasoline in relation to Diesel
Source: nach
Fachverband
der
Gas-
und Wärmeversorgungsunternehmen, Wien
1) 1)
1) Green house gas reduction by using natural gas;nearly 100 % reduction by using renewable SNG!
Environmental Benefits via CNG-Vehicles: Audi balanced mobility / e-gas project (12.05.2011)
Sustainable mobility with CNG vehicles powered with e-gas
e-gas: SNG via P2G-plant
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps
Award for Power-to-Gas - Concept: SolarFuel / ZSW / IWES
Award “ASUE” of the German Gas Industry in the field “Innovation and
Climate Protection”, 29.09.2010, Berlin
Agenda Part I: Power-to-Methanol / CO2 from Air Agenda Part II: Power-to-Gas (P2G)
Goal (P2G)SNG Production Routes from REP2G ConceptCO2 ResourcesConversion EfficiencyEnvironmental BenefitsResults from 25 kWe P2G Pilot PlantConclusions / Next Steps