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References:[1] A. Negoi, K. Triantafyllidis, V.I. Parvulescu, S.M. Coman, Catal. Today 223 (2014) 122-128.[2] L.S. Ribeiro, J.J.M. Órfão, M.F.R. Pereira, Green Chem. 17 (2015) 2973-2980.
Acknowledgements:This work was financially supported by: project POCI-01-0145-FEDER-006984 – Associate Laboratory LSRE-LCM funded by FEDER funds through COMPETE2020 - Programa Operacional Competitividade eInternacionalização (POCI) – and by national funds through FCT - Fundacao para a Ciencia e a Tecnologia.L.S. Ribeiro acknowledges her scholarship (SFRH/BD/86580/2012) by FCT.
VALORISATION OF BIOMASS: TRANSFORMATION INTO VALUE-ADDED PRODUCTS
Lucília S. Ribeiro1,*, José J. Melo Órfão1 and M. Fernando R. Pereira1
1 Laboratório de Processos de Separação e Reação - Laboratório de Catálise e Materiais (LSRE-LCM), Faculdade de Engenharia, Universidade do Porto, Portugal. *[email protected]
O2
CO2
H2O
C + O2 = CO2
2014 2039 2064 2089 2114
Coal
Gas
Oil
Impact of anthropogenic CO2 emissions
Increasing energy demand
Depletion of fossil fuel reserves
• Inexpensive• Renewable• Abundant source of carbon• CO2 neutral alternative
Biomass:
• Efficient utilization of bioresource material• Environmental friendliness• High selectivity to desired products• Less production of waste• Cost effectiveness
Catalytic process:
• Ease of catalyst separation after reaction• Reutillization of catalyst is possible
Heterogeneous catalyst:
Energy consumption has increased steadily over the last century as the world population has grown and more countries have becomeindustrialized.
Search of alternativerenewable resourcesfor the production ofchemicals and fuel
Cellulose is one of the most abundant form of biomass on Earth.
The efficient conversion of cellulose into target products allows to reduce CO2 emissionsand alleviates the energy crisis. It is the case of the one-pot hydrolytic hydrogenationof cellulose to sugar alcohols, specially sorbitol.
Sorbitol is an important platform molecule and can be used as sweetener, dispersing agentand humectant in pharmaceuticals, cosmetics, and textiles [1].
INTRODUCTION
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EXPERIMENTAL METHODS
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RESULTS
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Cat
alys
t Ru
Met
al p
has
e
CNT
Sup
po
rt
Incipient wetnessimpregnation
method
Activation:• thermal treatment → N2
•metal reduction → H2
Ru/CNT
CommercialMicrocrystalline Cellulose
Ball-milling
Reduce the crystallinity
Ce
llulo
se
Standard conditions :
•Treaction = 205 ºC
•PH2= 50 bar
•300 mL H2O
•750 mg of cellulose
•300 mg of catalyst
•150 rpm
Re
acti
on
Hydrolysis Hydrogenation
One-pot
Sweetener
Bioethanol
Isosorbide
PET additive
EG, PG
Antifreeze
1,4-Sorbitan
Surfactant
Lactic acid
Biodegradable plastics
Glycerol
Plastics
MIX-MILLING
Catalyst
(Ru/CNT)
Cellulose
0
20
40
60
80
Comercialmicrocrystalline
cellulose
Ball-milledcellulose
Mix-milledcellulose
Sele
ctiv
ity
to s
orb
ito
l(%
)
0
20
40
60
80
100
0 60 120 180 240 300
Co
nve
rsio
n(%
)
Time (min)
Mix-milledcellulose
Ball-milledcellulose
Commercialmicrocrystallinecellulose
Ball-milling
10 15 20 25 30
Inte
nsi
ty(a
.u.)
2θ
Commercialmicrocrystalline cellulose
Ball-milled cellulose
92%
23% Cry
stal
linit
yDecrease with
ball-milling
Ball-milling:
Increases cellulose conversion
Increases sorbitol selectivity
Mix-milling [2]:
Greatly increases cellulose conversion
and selectivity to sorbitol
Ball-milling
Mix-milling
Commercial
1 h of reaction
