Catalyzing a CO2-neutral Society

Mark Saeys, Laboratory for Chemical Technology, Ghent University

De KoninklijkeVlaamse Academie van

België voor Wetenschappen en Kunsten

De koolstofeconom ie

Cement

DakbekledingRamen

Kader raamIsolatiemateriaalBeton

Textiel bv. tapijt, gordijnen, …

Stalen chassis auto

Koetswerk auto

Uitlaat autoPleistermaterialen

Afwerking meubels:

kunstleder,

melamine,…

Radiatoren

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2

CO2 CO2 CO2

CO2

Martens et al. KVAB Standpunt 39

Carbon-based Society

Insulation materials

ConcreteRoofing Bricks

Windows

Heaters

Chassis car

Car exhaust

Textiles, curtains,…

Furniture

Paving Decoration Electronics

Fossiele koolstof

Reserves (ontginbaar)

Voorraden (nog niet ontginbaar)

< 2°C

Parijs akkoord 2 0 1 5

Uitstoot 2 0 0 0 – 2 1 0 0

1 9 0 0 Gt CO2

= 5 0 0 Gt C

Petroleum Teerzanden

en schalie olie

Aardgas Schalie gas Methaan-

hydraten

Steenkool Globale jaarlijkse

consumptieMartens et al. KVAB Standpunt 39

Fossil Carbon Reserves

Reserves (proven)

Reserves (known)

Tar Sands

Shale oilNatural Gas Shale Gas Methane

hydratesCoal Total allowed CO2

production

COP21, 2015

Emissions 2000-2100

1900 Gt CO2

Combustion

Milliseconds

Days to months

Millions of years

zon

CO2

CO2 Cycle: Kinetic / Catalytic challenge

sun

Renewable

energy sources

fuels

oil, gas,

coal

fossil

carbon reserves

plants

algae

Capture and StorageCCS: CO2 produced at point sources is captured

and sequestered in depleted oil and gas reservoirs

Take-back policy?

For every Fossil C atom taken from a reservoir,

one CO2 molecule should be taken back

Household Methane

$/Mwh in EU-28

Price of Renewable Energy

Wind Solar PV

CCU

Renewable Energy in the EU

© Energy-X

Methanol

Formic acid

Acetates

Methane

CO2Antibacteri

alNatural

Gas

Flavonoids

Metallurgy

Fuels Biodiesel

Carbon monoxide

Paint and Coatings

Detergents

PolyolsPoly-

urethane

CelluloseAcetate

Super-Dry

Reforming

CaproicAcid

C3-C6Alcohols

What can we do with CO2- UGent portfolio

4C

Centre for Advanced Process Technology

for Urban resource REcovery

Platform initiative that operates a

physical and virtual place to help

researchers, companies and government

to co-create and interact with each other

under three pipelines.

Bringing everyone together

Academia Industry

Renewable Energy Government

Scientific experts

Mark Saeys

AnnemieBogaerts

JanVaes

Investigate the conversion of CO2 to

solar fuels (methane and methanol)

Integration of new developments in

the production of solar hydrogen.

Design and synthesis of selective

catalysts active at milder reaction

conditions.

Design of effective CO2 capture and

separation technologies.

CatCO2RE: General Goal

-

+

Water

Hydrogen

Vapor phase electrolysis

H2

O2

Light

Dark

Air (water vapour)

+

-e-

Solar-to-Hydrogen: CatCO2RE

1-2 g H2/m2 hr !

SOLAR ENERGY+ CO2 + H2O

CATALYSIS

SOLAR FUELS

CO2

Storage of Solar Photons

Molecule Heat

(kJ/mol C)

H2

eq.

Fraction H2

energy stored

Hydrogen -240 100

Methanol -680 3 94

Diesel -640 3 89

Glucose -450 2 94

Storage of Solar Photons: Audi and Sunfire

Power 13 kWh/kg gasoline x 0.5 kg/s ~ 25 MW

Energy 50 kg gasoline = 2.3 GJ

Solar? 1.4 kW/m2 -> 460 hours on 1 m2 for 2.3 GJ

Electrical? Power plant ~ 500 MWRakesh Agrawal, Purdue

Liquid fuels: Convenient, High energy-density

+ 40 kg solar fuel

+ 100 kg hydrogen

+ 600 kg batteries

60 kg gasoline1300 kg

Modestino et al., Ener. Env. Sci., 2014

Solar-to-Hydrogen: Optimistic study

Cost of materials

Electrolyzer: 10%

Si PV: 90%

Total: 0.75 €/kg H2

-> 0.15 €/l solar fuel

Market: 0.25 €/l

CO2 Materials

20th March 19 │ Carbon4PUR

Steel

production

Flue gas

CO/CO2

Conditioning

Polyol 2

Polyol 1

Polyol 3

Polyol 4

CO2-based foams

CO-based coatings

CO-based foams

CO2-based coatings

Building block 1

Building block 2

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 768919 7

Methodology

PRODUCTS & APPLICATION BUILDING BLOCKS / INTERMEDIATES CO/CO2

Turning industrial waste gases

into valuable polyurethanes

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 768919

Insulation board

4C: CO2 to Acrylates

Large growing market: 5 million t/yeara

Main ingredient used for superabsorbent polymers

Early stage

Low TON

Use of stoichiometric bases

aByrne. (2016) IHS Chemical Bulletin, 14-15

Super-Dry Reforming

CH4

3 CO2

2 H2O

inert

4 CO

inert

Reducer Oxidizer

Ni

Fe/FeO

CaCO3

Ni

Fe3O4

CaO

CH4 + 3 CO2→ 4 CO + 2 H2OExperiment at our lab:

• T = 1023 K

• CH4:CO2 = 1:3

• 25 cycles

Buelens et al. (2016) Science

ACID RAIN

SO2

A Carbon-free economy is unthinkable

Objective: CO2-neutral society

Natural photosynthesis is too slow

to close the carbon cycle

Solar-driven chemical technology

needs to be implemented

Conclusions - KVAB

Preserve carbon-based standard-of-living

Introduce CO2 and Renewable Energy in the

fuel and chemicals cycle

Need for a Positive Message

𝟎. 𝟔 𝒕 𝑪𝑶𝟐+ 𝟏 𝒕 𝑭𝒆𝟎. 𝟔 𝒕 𝑪𝑶𝟐+ 𝟏 𝒕 𝑭𝒆

CO2 Abatement in the Steel Industry

Ideally:

𝟑 𝑪 + 𝟐 𝑭𝒆𝟐𝑶𝟑 → 𝟑 𝑪𝑶𝟐+ 𝟒 𝑭𝒆

Not favored at room temperature

Thermodynamic equilibrium limitations

In reality:

𝟑 𝑪 + 𝟐 𝑭𝒆𝟐𝑶𝟑 → 𝟑 𝑪𝑶𝟐+ 𝟒 𝑭𝒆

Thermodynamically favored over 1000oC

The full conversion of C to CO2 is inhibited by the redox equilibrium:

𝑪 + 𝑶𝟐 → 𝑪𝑶𝟐

Exothermic reaction

CO production favored over 700oC

𝑪 + 𝑪𝑶𝟐 ↔ 𝟐 𝑪𝑶

CO2 Abatement in the Steel IndustryPower-to-What?Where should we use renewable electricity first?

Sternberg, Bardow et al. (2015). Power-to-What? Energy & Environmental Science

Global warming (GW) impact reduction.

CO2 Abatement in the Steel Industry

Electricity

H2Electrolysis

Carbon Capture,

Utilization and

Storage (CCUS)

Carbon Capture and

Utilization (CCU)

Hydrogen-based

Steel-making (HST)

Carbon-based Steel-making

CO2

COH2

CO2 for storage

CO/CO2 to

methanol/ethanol

Carbon-based Steel-making (CST)

Power Plant

BFG BOFG

Electricity

CO2/N2Air

Iron Ore

Liquid Steel

CST

Coal

● C-based steel plant.

● Electricity consumption.Grid Emission Intensity = 0.25 t CO2/MWh

IEA (2013). Iron and Steel CCS Study (Techno-Economics Integrated Steel Mill).

Carbon Intensity = 2.1 t CO2/MWh

Carbon Capture, Utilization and Storage (CCUS)

SEWGS

CO2 storage

BFG BOFG

N2/H2

separation

Methanol synthesis

N2

H2/N2

H2

CO2Steam

Methanol

CST CCUS

● C-based steel plant.

● CO2 compression for storage.

● Treatment of the steel mill gases and alternative methanol production.

● CO2 reduction by storage and/or replacement of conventional methanol production.

● Electricity consumption.

Iron Ore

Coal

Liquid Steel

Grid Emission Intensity = 0.25 t CO2/MWh

IEA (2013). Iron and Steel CCS Study (Techno-Economics Integrated Steel Mill).

DECHEMA (2017). Low carbon energy and feedstock for the European chemical industry.

Van Dijk et al. (2017). Energy Procedia

Electricity

H2

Carbon Capture and Utilization (CCU)

SEWGS

Electrolysis

BFG BOFG

N2/H2

separation

Methanol synthesis

N2

H2

CO2

Steam

Methanol

CST CCUS CCU

● C-based steel plant.

● Water electrolysis.

● CO2 compression for storage.

● Treatment of the steel mill gases and alternative methanol production.

● CO2 reduction by storage and/or replacement of conventional methanol production.

● Electricity consumption.

Iron Ore

Coal

Liquid Steel

H2/N2

Grid Emission Intensity = 0.25 t CO2/MWh

Häussinger et al. (2011). Hydrogen Production, vol. 18, pp. 249-307.

Liquid Steel

Hydrogen-based Steel-making (HST)

● C-based steel plant.

● H2-based steel plant.

● Water electrolysis.

● CO2 compression for storage.

● Treatment of the steel mill gases and alternative methanol production.

● CO2 reduction by storage and/or replacement of conventional methanol production.

● Electricity consumption.

H2

Electrolysis

Electricity

CST CCUS CCU HST

Iron Ore

Coal

Grid Emission Intensity = 0.25 t CO2/MWh

Volpatti, A. et al. (2013). Energiron Direct Reduction

Duarte, P. (2019). Hydrogen-based steelmaking.

Hertrich-Giraldo, A. et al. (2019) Energiron Direct Reduction Technology.

Renewable Electricity in the Steel industry

Carbon-based Steel-making

Wind ElectricityCarbon intensity = 0.01 t CO2/MWh

DECHEMA (2017). Low carbon energy and feedstock for the European chemical industry.

IEA (2019). Exploring Clean Energy Pathways.

Conclusions CCUS route:

Reduction by 50% of the CO2 emissions with an electricity demand of 1.1 MWh/t l.s when a grid of 0.25 t

CO2/MWh is used.

Maximum emissions reduction potential of 70% when renewable electricity is utilized (0.01 t CO2/MWh).

CCU route: For a grid intensity of 0.05 t CO2/MWh, the CCU scenario provides a larger CO2 emissions reduction than the

CCUS route.

It requires 8 times more electricity than the CCUS route (8.9 MWh/t l.s.)

A maximum reduction of 85% of CO2 emissions is possible if renewable electricity is utilized in this route.

Hydrogen-based steel-making route: This route abates a larger share of CO2 emissions than CCUS route at GEIs lower than 0.11 t CO2/MWh.

This process requires a complete reconstruction of the steel plant and requires 4 times more electricity than the

CCUS route (4.2 MWh/t l.s.).

A maximum emissions reduction potential of 85% when a renewable grid is used (0.01 t CO2/MWh) is possible.

Either storage capacity or renewable electricity are necessary for the abatement of CO2 in the

steel industry.

LABORATORY FOR CHEMICAL TECHNOLOGY

Technologiepark 125, 9052 Ghent, Belgium

E info.lct@ugent.be

T 003293311757

https://www.lct.ugent.be