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2014 INTERNATIONAL WORKSHOP ON ENVIRONMENT AND ALTERNATIVE ENERGYIncreasing Space Mission Resiliency through Sustainability
22nd October 2014
Production of renewable synthetic
fuels from electricity using
ELECTROFUEL® concept
Luís Guerra ; João Gomes ; Jaime Puna ; José Rodrigues
Contents…Contents…Contents…Contents…
• ELECTROFUEL® concept
• Syngas applications
• Syngas to liquid fuels
• Preliminary tests
• Future work
• Conclusions2
Synthetic Fuels…Synthetic Fuels…Synthetic Fuels…Synthetic Fuels…
… are able to cut oil dependence
… contribute to reach low carbon targets• Without the need for heavy investments to replace the existing platform
… allow the development of more attractive technologies to follow their learning path• Hydrogen or Fuel Cells (mature technology)
3
Water Electrolysis
Renewable Energy
Carbon
Source
ELECTROFUEL®
CONCEPT
Power and
Carbon to
4
SYNGAS
Diesel
(Fischer-TropschSynthesis)
Methanol
(CO/CO2hydrogenation)
Methane
(Sabatier Process)
Gasoline
(Mobil process)
DME
(TopsoeTechnology)
to Liquid fuel
Syngas production by ELECTROFUELSyngas production by ELECTROFUELSyngas production by ELECTROFUELSyngas production by ELECTROFUEL®®®®
• One step from water electrolysis…
… without separation of gases
…with the use of carbon/graphite plates as electrodes and alkaline electrolyte
• Oxygen, on the anode, reacts with carbon from the electrode, • Oxygen, on the anode, reacts with carbon from the electrode, producing CO and CO2
• C + 2 H2O � CO2 + 4 H+ + 4 e-
• C + H2O � CO + 2 H+ + 2 e-
• Hydrogen is released directly from the cathode• H2O + 2 e- � 2 HO- + H2
• Syngas is then formed and can be used as a raw
material for synthetic fuel production5
Syngas and its Applications…Syngas and its Applications…Syngas and its Applications…Syngas and its Applications…
6
Advantages of this technology…Advantages of this technology…Advantages of this technology…Advantages of this technology…• Use of renewable energy as power source
• Solar or wind…
• Electrolyzers: cheap and easy to build
Able to compete with the conventional technologies:• Able to compete with the conventional technologies:• Steam reforming, coal gasification…
• Renewable energy:• Stored in liquid state (diesel, gasoline) at a competitive cost
• Due to its simplicity:• economically feasible in small scale units7
SyngasSyngasSyngasSyngas to Liquid Fuels…to Liquid Fuels…to Liquid Fuels…to Liquid Fuels…
• Through a catalytic reaction
• Highly exothermic• Highly exothermic
• Intensive research to improve reaction conditions:• Pressure, temperature, catalyst activity…
8
• Project partner:• Working on the best catalyst to produce methanol
• CuO+ZnO+Al2O3+MgO � Reference catalyst for testing
SLURRY REACTORSLURRY REACTOR
9
ELECTROFUELELECTROFUELELECTROFUELELECTROFUEL®®®® Reactor…Reactor…Reactor…Reactor…
Water with
Fuel ReactorPurification
ELECTROFUEL®
vesselElectrolizer
electrolyte
10
ElectrolyzerElectrolyzerElectrolyzerElectrolyzer Diagram…Diagram…Diagram…Diagram…
Plates for adjusting the distance between electrodes
Anode
Sidesection
Electrodes
Anode
Cathode
Frontsection
Vessel
11
Laboratory set-up12
Where are we?Where are we?Where are we?Where are we?
• Provisory Patent Registration
• Proof concept � Syngas
• COMPETE: Portuguese Innovation Incentive Schemes (Project 38940)
• Laboratory models undergoing:• Optimization and evaluation studies
13
Where are we headed?Where are we headed?Where are we headed?Where are we headed?• Catalytic reactor to produce Methanol and DME
• First Industrial Prototypes tests:• 1 L/h and 10 L/h of Methanol / DME
• Motorization tests
• Scale-up to 100 L/h of Methanol / DME
• Demonstration plan
• Patent protection14
Preliminary Tests…Preliminary Tests…Preliminary Tests…Preliminary Tests…Conditions:
-V = 20 V- NaOH 0.06 M- Electrolyzer:
1 cell2 graphite electrodesdist. 6 mm1200
1500
1800
2100
Applied
Curren
t (m
A)
-T = 25 ºC- P = 1 atm
0
300
600
900
1200
0 10 20 30 40 50 60 70 80 90 100 110
Applied
Curren
t (
Reaction Time (min)
I ≈ 550 mA
15
0.45
0.50
0.55
0.60
4.5
5.0
5.5
6.0
Consumed
Energy
(Wmin/mL)
Electric Potential (V)
Conditions:
- NaOH 0.06 M- Electrolyzer:
1 cell2 graphite electrodesdist. 6 mm
-T = 25 ºC- P = 1 atm
0.30
0.35
0.40
0.45
3.0
3.5
4.0
4.5
0 10 20 30 40 50 60 70 80 90 100 110
Consumed
Energy
(Wmin/mL)
Electric Potential (V)
Applied Current (mA)
V = 4 V
16
Conditions:
-V = 4 V- Electrolyzer:
1 cell2 graphite electrodesdist. 6 mm
-T = 25 ºC- P = 1 atm
0.30
0.35
0.40
0.45
0.50
Consumed
Energy
(Wmin/mL)
0.10
0.15
0.20
0.25
0.30
0.00 0.10 0.20 0.30 0.40 0.50 0.60
Consumed
Energy
NaOH concentration (M)
[NaOH] = 0.4 M
17
Conditions:
-V = 4 V- NaOH = 0.4 M- Electrolyzer:
1 cell2 graphite electrodes
-T = 25 ºC- P = 1 atm
Distance between electrodes: 4 mm1450
170019502200245027002950
Applied
Curren
t (m
A)
electrodes: 4 mm
200450700950
12001450
3 4 5 6 7 8 9 10 11 12
Applied
Curren
t
Distance between electrodes (mm)
18
• Graphite Electrodes Loss
Conditions:
-V = 4 V- NaOH 0.4 M- Electrolyzer:
1 cell2 graphite electrodesdist. 4 mm
- Formation of nanocarbon particles
- Anode ≈ 1.5 % less mass after a 7 hours reaction
- Some of the mass lost is gained on the cathode
dist. 4 mm-T = 25 ºC- P = 1 atm
19
Conditions:
-V = 4 V- NaOH = 0.4 M- Electrolyzer:
1 cell2 graphite electrodesdist. 4 mm
-T = 25 ºC- P = 1 atm
10
12
14
16
20
22
24
26
CO compositions (%)
composition (%)
20
0
2
4
6
8
10
12
14
16
18
0.5 1.0 1.5 2.0
O2e CO compositions
CO
2co
mposition
Applied Current (A)
CO2
O2
CO
• Gas analysis
• With a best optimization we were able to achieve an interesting composition of syngas as follows (dry basis):
H2 70 %
CO 10 %
CO2 16 %
O2 4 %
Others (hydrocarbons) ≈ 0 %
21
• Steel + Graphite vs. Graphite
22
Electrodes Graphite Steel + Graphite
H2 70 % 58 %
CO 10 % 4 %
CO2 16 % 28 %
O2 4 % 10 %
Others (hydrocarbons) ≈ 0 % ≈ 0 %
Further tests still onFurther tests still onFurther tests still onFurther tests still on----going …going …going …going …
• Hydrocarbons were found on the gas analysis
• Temperature influence is not yet fully explored
• Pressure influence is not yet fully explored• Pressure influence is not yet fully explored
• The destination of the nanocarbon particles:• Steam reforming…
• Use of catalysts spread in the electrolyte to improve syngascomposition• Vanadium…
23
To summarize…To summarize…To summarize…To summarize…
• Water electrolysis: renewable energy as electricity, carbon/graphite electrodes, without separation of gases and an alkaline electrolyte � syngas
• We reached 10 % of CO and 70 % of H2, with 4 % of O2We reached 10 % of CO and 70 % of H2, with 4 % of O2
• Laboratory models for syngas production undergoing:• Optimization and evaluation studies �Temperature, pressure…
• Improve reaction conditions of methanol production:• Pressure, temperature, catalyst activity…
24
PROJECT SYM
QREN 38940
PARTNERS:
Thank You For Your Attention…Thank You For Your Attention…Thank You For Your Attention…Thank You For Your Attention…
25