cascatbel newsletter · cascatbel newsletter page 2 hydroxyapatite, an exceptional catalyst for the...

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CONTENT: CASCATBEL Project 1 2 nd 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 FEBRUARY 2015 ISSUE 3 www.cascatbel.eu PAGE 1 C ASCATBEL is a European Commission’s Seventh Framework programme Project. It started in November 2013 and will run for four years. The project brings together 17 partners from 10 dierent European countries. CASCATBEL aims to design, opƟmize and scaleup a novel mulƟ‐step process for the producƟon of secondgeneraƟon liquid biofuels from lignocellulosic biomass in a costecient way through the use of nextgeneraƟon high surface area tailored nanocatalysts . The strategy proposed in CASCATBEL will lead to the preparaƟon of advanced biofuels having composiƟon and properƟes very similar to petroleumderived fuels. This is a very relevant advantage regarding the commercial implementaƟon of this technology, as it would not require any signicant changes in the already exisƟng 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 2 nd Governing Board Meeting in Zürich The 2 nd Governing Board MeeƟng took place on 30th October 2014 in Zürich, Switzerland. The meeƟng was organized by ETHEidgenoessische Technische Hochscule and members of 17 partners of the consorƟum parƟcipated. The following issues were discussed: Current status of the project and management issues Main achievements and future acƟviƟes in WP2, WP3, WP4, WP5 and WP8 Any other bussiness Next Governing Board meeƟng will take place in Brussels, Belgium on 28th April, followed by First Project Review on 29 th April.

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Page 1: CASCATBEL Newsletter · CASCATBEL NEWSLETTER PAGE 2 Hydroxyapatite, an exceptional catalyst for the gas-phase deoxygenation of bio-oil by aldol condensation H ydroxyapatites with

  

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. 

Page 2: CASCATBEL Newsletter · CASCATBEL NEWSLETTER PAGE 2 Hydroxyapatite, an exceptional catalyst for the gas-phase deoxygenation of bio-oil by aldol condensation H ydroxyapatites with

  

 

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. 

Page 3: CASCATBEL Newsletter · CASCATBEL NEWSLETTER PAGE 2 Hydroxyapatite, an exceptional catalyst for the gas-phase deoxygenation of bio-oil by aldol condensation H ydroxyapatites with

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. 

Page 4: CASCATBEL Newsletter · CASCATBEL NEWSLETTER PAGE 2 Hydroxyapatite, an exceptional catalyst for the gas-phase deoxygenation of bio-oil by aldol condensation H ydroxyapatites with

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 

Page 5: CASCATBEL Newsletter · CASCATBEL NEWSLETTER PAGE 2 Hydroxyapatite, an exceptional catalyst for the gas-phase deoxygenation of bio-oil by aldol condensation H ydroxyapatites with

www.cascatbel .eu

E-mail: [email protected] C A S C A T B E L N E W S L E T T E R

P A G E 5