“Eco-friendly biorefinery fine chemicals from CO2 photocata-lytic reduction”

Guido SaraccoPolitecnico di TorinoDipartimento di Scienza Applicata e TecnologiaE-mail: guido.saracco@polito.it

Potential of carbon-free energy sources

Source: Basic Research Needs for Solar Energy Utilization, DOE 2010

3

Sun to chemicals routes

Bio-fuels/chemicals

Solar fuels/chemicals: water photolysis and CO2 reduction to fuels/chemicals

+ H2 O + H2 + O2

CO2 Fuels, chemicals

4

New scenario for sustainable chemical production: integration of natural and artificial photosynthesis routes

G. Centi, S. Perathoner, ChemSusChem 2014 (in press)

Crude Oil Natural Gas

Naphtha

REFINING

EthanePropane Methane

PROCESSING

Propylene EthyleneC4 streamBenzeneTolueneXylenes

CATALYTIC REFORMING H2

Syngas

STEAM REFORMING

Methanol

MTBE

Formaldehyde

Fuels

Phenolic resins

Polyurethanes

Methyl‐methacrylatePo

lymers& m

at.

Poly‐ethylene

Poly‐propylene

Acrylic acid Ethylbenzene

Styrene

Ethylendichloride

Styrene

Ethylenoxide

Ethanolamines

Ethylenglycols

Ethyl‐alcohol

Polymers& m

at.

Ethylacrylate

Vinylacetate

Ethylacetate

Acetic acid

Acetaldehyde

Acrylonitrile

Cumene

Phenol

Propylene oxide

Propylen glycols

Isopropanol

Acetone

Solven

ts, C

hemicals

Butadiene

Isobuthylene

N‐Butenes

Higher olefins

Fuels, 

Lubrificants

Detergents, agrochemicals

Polymers

& m

at.

OLEFINS

STEAM CRACKING

AROMATICS

Ethylbenzene

Styrene

Polymers& m

aterials

Cyclohexane

Nylon

Cumene

Polycarbonates

Phenolic resins

Alkylbenzenes

Solvents, Chemicals

Toluen‐diisocyanate

Polyurethane

p‐xylene

Polyesters

o‐xylene

Plasticisers

Current Petrochemicals Flowchart

H2O

CO2

RENEWABLE ENERGY

Lignin

Ethanol

Butanol, 2,3 Butanediol

Sugars

New scenario for sustainable chemical production

Glycerol

ENERGY (FOR CHEMICAL PROCESSES)

(H2)

BIOGAS

5

Competition with fossil sources is very hard!

Production of high‐added value chemicals along with biofuels may render the biorefinery approach competitive

6

Methanol production cost from different sources

Galindo Cifre & Badr, Energy Conv. & Management 48 (2007) 519–527

7

The main goal: exploit everything to achieve cost effectiveness

Hexose

Pentose

By products(F, HMF, humins)

Fermentation

Dehydration Furfural

Gasification

Hydrolysis 

Depolymeri‐

sation

CO2(conc.)

H2

CO2

Ethanol

CH4Lignin

H2

O

benzene, phenol, 

oligomers…

H2

O

Farnasene

…

The Eco2CO2

chemical platform

Partnership

Nr Name Logo/ key investigators Nation Main roles in the project

1 Politecnico di Torino Prof. G. Saracco Prof. J. Barber Prof. B. Onida

IT Coordination, water-splitting

catalyst and electrode develop-ment, modelling, LCA

2 Delft University of Technology

Prof. F. Kapteijn Prof. M. Makkee

NL Development of CO2 reduction catalysts with special reference

to MOFs

3 European Research Institute of Catalysis

Prof. G. Centi

Prof. S. Perathoner BE

CO2 reduction catalysis. PEC reactor design

Furfural derivatives

4 Centro Tecnologico de la Quimica de Catalunya

Dr C. Claver ES Chromophores development

Lignin derivatives

5 Chemtex Italia SpA Dr. A. Frattini Dr. S. Pescarolo

IT System modelling, Process design, Market analysis

6 Avantium Chemicals BV Dr. Ed de Jong

NL Photocatalyst development; Perfumes from furfurals

7 Solaronix SA Drs. T. & A. Meyer CH Electrodes and electrodes assembly development

8 Repsol SA

Dr P. De Fruitos Escrig

ES CO2 reduction catalysis Lignin derived chemicals

9 IREC J. Salvado, C. TorresES Lignin direct conversion

treatments

Concept and project objective(s)

Concept and project objective(s)

•The key objective ot the project will be to provide evidence that fine chemical products can be effectively produced in a cost-competititve way comparable to their synthesis from petroleum derivatives. In any case, production rates of 100 g product/h

in pilot reactors will need to be attained.

•A targeted efficiency exceeding 6% for this conversion process

is set, calculated, per unit surface area exposed, as the ratio between the higher heating value of the produced methanol and the overall incoming solar power. Model calculations, presented in the impact section, show that this con-cept has the potential to exceed 10% conversion efficiencies

•The perspected system durability

will exceed 10.000 h

lifetime. A 10x10 cm2

prototype will be manufac-tured and tested by the end of the project

to prove the achievement of the above targets and pave the way to subse-quent exploitation of the technology. The test duration

will be at least 1000 h

in the last six months of the project.

•To disclose wide potential application opportunities, the above targets must be reached without using expensive noble metals or materials

and via assembling techniques

amenable for mass production.

Direct synthesis of solar methanol

Carbon dioxide Water Solar Methanol

Sun+ + =

Concept and project objective(s)

To carboxylases

CO2

reduction at TUDelft

η

= 0.14 %

Possible alternative route

CO2

solubility is an issue!

Second alternative: pressurized CO2

solutions to syngas

Methanol based reaction pathways

The need of a breakthrough:Have you ever seen a supersonic bird?

(cartoons apart)

Competing technologies are running fast (PV)

Evolution of record solar-to-fuel efficiencies

Example: the Van de Kroel system (~5% efficiency)

…we have to go radically beyond this!

Nature Communications, 4, 2195 (2013)

Potential keys to success

- Exploit semiconductors

- Keep them away from water

- Operate at high pressures (if CO+H2

is the target)

- Exploit sun concentration

- Exploit heat from the sun

Pioneering effort at F-ISE

18,2 % STH efficiency

Multi-junction flexibility (0,5-5V)

Concentrated vs. non-concetrated photovoltaics

A new key partner on board

Combining the best solar-thermal with the best concentrated-PV

+ -

e-

CO,H2O2

H+

CO2ladenwater

MJ cell

anode cathode

sunconcen-trator

P=15 bar

T up to150°C

outletwater

A new project just started: Cardiosol

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CO2 as raw material …a better way to store CO2

than this!

…Thank you for your attention!