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

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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…

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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…

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• Project partner:• Working on the best catalyst to produce methanol

• CuO+ZnO+Al2O3+MgO � Reference catalyst for testing

SLURRY REACTORSLURRY REACTOR

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ELECTROFUELELECTROFUELELECTROFUELELECTROFUEL®®®® Reactor…Reactor…Reactor…Reactor…

Water with

Fuel ReactorPurification

ELECTROFUEL®

vesselElectrolizer

electrolyte

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ElectrolyzerElectrolyzerElectrolyzerElectrolyzer Diagram…Diagram…Diagram…Diagram…

Plates for adjusting the distance between electrodes

Anode

Sidesection

Electrodes

Anode

Cathode

Frontsection

Vessel

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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

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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

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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

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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)

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• 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

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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

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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 %

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• Steel + Graphite vs. Graphite

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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…

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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…

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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…

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