C O N T E N T :
CASCATBEL
Project 1
2nd Governing
Board Meeting in
Zürich
1
Hydroxyapatite,
an exceptional
catalyst for the
gas-phase
deoxygenation of
bio-oil by aldol
condensation
2
Ketonization of
Carboxylic Acids
in Biomass Con-
version over
TiO2 and ZrO2
Surfaces: A DFT
Persperctive
3
Deliverables 4
Events 4
Partners 5
CASCATBEL Newsletter F E B R U A R Y 2 0 1 5
I S S U E 3
www.cascatbel.eu
P A G E 1
C ASCATBEL is a European Commission’s Seventh Framework programme Pro‐
ject. It started in November 2013 and will run for four years. The project
brings together 17 partners from 10 different European countries. CASCATBEL aims to
design, op mize and scale‐up a novel mul ‐step process for the produc on of second‐
genera on liquid biofuels from lignocellulosic biomass in a cost‐efficient way through
the use of next‐genera on high surface area tailored nano‐catalysts . The strategy pro‐
posed in CASCATBEL will lead to the prepara on of advanced biofuels having composi‐
on and proper es very similar to petroleum‐derived fuels. This is a very relevant ad‐
vantage regarding the commercial implementa on of this technology, as it would not
require any significant changes in the already exis ng infrastructures and engines.
CASCATBEL PROJECT
On 27-28th of February 2014, 1st CASCATBEL Governing Board meeting took place in Hamburg, Germany. The meeting was organized by TUHH and representatives of the 17 partners of the consor-tium participated in it.
The following main issues were discussed:
- Current status of the project and manage-ment issues, including deliverables, publications and events organization.
CASCATBEL’s 2nd Governing Board Meeting in Zürich
The 2nd Governing Board Mee ng took place on 30th
October 2014 in Zürich, Switzerland.
The mee ng was organized by ETH‐Eidgenoessische Tech‐
nische Hochscule and members of 17 partners of the con‐
sor um par cipated.
The following issues were discussed:
‐ Current status of the project and management issues
‐ Main achievements and future ac vi es in WP2, WP3,
WP4, WP5 and WP8
‐ Any other bussiness
Next Governing Board mee ng will take place in Brussels,
Belgium on 28th April, followed by First Project Review on
29 th April.
C A S C A T B E L N E W S L E T T E R P A G E 2
Hydroxyapatite, an exceptional catalyst for the gas-phase deoxygenation of bio-oil by aldol condensation
H ydroxyapatites with high surface concentration of calcium exhibit outstanding activity, se‐lectivity, and stability in the gas‐phase condensation of propanal in comparison with well‐
established base catalysts. These abundant and low‐cost materials can be attractively used for the deoxygenation of bio‐oil, contributing to the sustainable manufacture of renewable second‐generation bio‐fuels. The production of second‐generation biofuels from pyrolysis oil comprises an intermediate solution for the partial substitution of existing fossil‐based feedstocks(1) A major cu‐rrent challenge involves the development of efficient routes to reduce the high oxygen content of the crude bio‐oil (e.g. 10–50 wt%), which impedes its direct application in modern combustion en‐gines due to the associated low heating value, chemical instability, and corrosiveness (2). Although the required specifications can be met through conventional hydrodeoxygenation, this approach is impractical due to the excessive consumption of expensive hydrogen (3). Alternatively, the deoxygenation of intrinsically reactive bio‐oil constituents can be attractively exploited through intermediate upgrading treatments to decrease the subsequent hydrogen demand, while simulta‐neously converting lower‐boiling point fractions into gasoline‐range molecules (4). In particular, aldol condensations draw attention due to the large aldehyde fraction of bio‐oil (up to 20 wt%). This class of reaction can be catalysed by solid bases such as alkali‐metal containing zeolites,(5 )alkaline‐earth metal oxides, (6) hydrotalcites, (7) and alkaline‐activated high‐silica zeolites. (8)Herein, it is expected that catalyst deactivation due to coke formation can be minimised by mode‐ration of the basic strength (6).
E. G. Rodrigues, T. C. Keller, S. Mitchell and J. Pérez‐Ramírez*
This journal is © The Royal Society of Chemistry 2014,, publiished on 02 September 2014
CASCATB
EL PUBLICATIONS
P A G E 2
Figure 1. (a) Atomic structural representa on, EDX maps evidencing the macroscopic distribu on of (b) calcium and (c)
phosphorus, (d) SEM and (e) TEM micrographs of the par cle and crystal morphology, and (e, inset) selected area elec‐
tron diffrac on pa ern of the stoichiometric HA.
E-mail: [email protected]
P A G E 3
Ketonization of Carboxylic Acids in Biomass Conversion over TiO2 and ZrO2 Surfaces: A DFT Perspective
P A G E 3
C arboxylic acids play a fun‐damental role in the trans‐
forma on of biomass into liquid fuels
and other useful chemicals. In order to
reduce the O/C content of biofuels, car‐
boxylic acids need to be decomposed by
decarboxyla on, dehydroxyla on, or de‐
carbonyla on unimolecular reac ons, or
they need to be converted into ketones
via complex bimolecular reac on mecha‐
nisms. Ketoniza on, that is, the transfor‐
ma on of carboxylic acids into ketones,
carbón dioxide, and water, is promoted
by heterogeneous catalysts based on oxide ma‐
terials. Among the most ac ve catalysts are ta‐
nia and zirconia surfaces. In recent years, a large
body of experimental data has been complemen‐
ted by specific inves ga ons performed with
first‐principles electronic structure calcula ons
based on density func onal theory (DFT). In this
review, I discuss the present level of understan‐
ding of the bonding modes of carboxylic acids (ace c acid in par cular) on the TiO2 and ZrO2 sur‐
faces as obtained from DFT calcula ons. Enoliza on and ketoniza on reac on mechanisms de‐
termined at the DFT level on TiO2 and ZrO2 surfaces are also discussed, and the results are
analyzed in view of the experimental evidence.Finally, the role of supported metal par cles, of
the redox proper es of the oxide catalyst, and the nature of the ac ve sites on the surface of ‐
tania and zirconia are discussed.
Gianfranco Pacchioni* Dipar mento di Scienza dei Materiali, Universita di Milano‐Bicocca, Via R. Cozzi, 55,
I‐20125 Milano, Italy
CASCATB
EL PUBLICATIONS
Figure 1. Some possible adsorp on geometries of ace c acid on (a) TiO2 ru le (110) surface, molecular monoden‐tate structure; (b) TiO2 ru le (110) surface, dissocia ve bidentate bridge structure. Violet (Ti), pink (O), black (C), and white (H). Distances in Å. Adapted from ref 55. © TiO2 anatase (101) surface, molecular monodentate structure; (d) TiO2 anatase (101) surface, dissocia ve bidentate bridge structure; (the posi on of dissociated H is not indicated; other structures, not shown, do also exist). Red (surface O); orange (acetate O); blue (Ti); black (C); pink (H). Adapted from ref 56.
E-mail: [email protected] P A G E 4
CASCATBEL DELIVERABLES SUBMITTED UP TO NOW
DEL. TITLE DATE
D1.1 Report on the availability of biomass resources in the EU 28/02/2014
D1.2 Supply and characteriza on of six representa ves biomass types 30/06/2014
D2.1 Catalyst samples for laboratory scale tests: prepara on and basic characteriza on 31/01/2015
D5.1 Report on the biomass pyrolysis tests at laboratory scale 30/09/2014
D8.1 Assessment of the reference process 31/10/2014
D8.2 Assessment of the results obtained at laboratory scale in biomass pyrolisys to aid in
selec on
31/10/2014
D10.1 Updated dissemina on plan 31/01/2014
D10.2 Standardiza on plan 31/03/2014
D10.4 Summer school for training of young researchers on biomass conversion technologies 30/06/2014
D10.3 Results exploita on strategy 31/03/2014
D10.5 Highlights of CASCATBEL’s annual progress for public dissemina on 31/10/2014
D11.1 Project Website 31/01/2014
P A G E 4
UPCOMING RELATED EVENTS EVENT PLACE DATES
Workshop on the Impact of the SPIRE PPP projects Brussels, Belgium 21‐22 April 2015
23rd European Biomass Conference and Exhibi on (EUBCE 2015)
Viena, Austria 1‐4 June 2015
EuroNanoForum 2015 Riga, Latvia 10‐12 June 2015
Nanotexology 2015 Thessaloniky, Greece 4‐11 July 2015
IEA Bioenergy Conference 2015 Berlin, Germany 27‐28 October 2015
Workshop on Layered Materials Trest, Czech Republic 15‐19 September 2015
Interna onal Congress and Expo on Biofuels & Bioenergy Valencia, Spain 25‐27 August 2015