Vol.:(0123456789) 1 3
Topics in Catalysis
https://doi.org/10.1007/s11244-019-01176-z
ORIGINAL PAPER
How to Valorize Peanut Shells by a Simple Thermal‑Catalytic Method
Carla S. Fermanelli
1
· Emilce D. Galarza
1
· Liliana B. Pierella
1
· María S. Renzini
1
· Clara Saux
1
© Springer Science+Business Media, LLC, part of Springer Nature 2019
Abstract
In this work, a simple thermal-catalytic system was used to valorize peanut shells (Arachis hypogaea), the residual biomass
from the peanut industry. To accomplish this purpose, tin modifed MEL zeolites were synthesized to catalyze pyrolysis
vapors reactions in order to improve bio-oil quality. The processes were conducted at 500 °C for 10 min, with biomass-to-
catalyst ratio of 1:1. Proximate, ultimate and elemental analyses of the peanut shells were carried out. Biopolymer compo-
sition and HHV were also determined. Thermal decomposition behavior of the raw material was assessed by TGA/DTG
analysis. Tin was incorporated to the zeolite matrix by the wet impregnation method to obtain loads of 2, 5, 7 and 10 wt%.
All the catalysts were characterized by XRD, TPR, FTIR and BET surface area. Liquid products composition was determined
by GC–MS. The material with 5 wt% of tin showed the best results. The optimal combination of Lewis and Brönsted acid
sites in this catalyst promoted the necessary reactions to enhance bio-oil quality. In this sense, hydrocarbons selectivity in
the presence of the 5 wt% tin zeolite was ten times the one reached in the absence of catalysts. Likewise, 5-hydroxymethyl-
furfural formation was favored, obtaining the highest selectivity with the same metal load on the catalyst.
Keywords Biomass valorization · Pyrolysis · Residual biomass · Tin · ZSM-11
1 Introduction
Considering that the term biomass includes all the organic
materials that derive from plants, and that plants are the
responsible to convert CO
2
into organic matter by photosyn-
thesis, it is possible to close the carbon loop when biomass
is employed as source of energy or chemicals [1]. Particu-
larly, when biomass wastes are employed as raw material,
the environmental advantage is improved.
In this paper, we propose the valorization of peanut
shells, since Argentina is one of the main global producers
of this legume. In our country, more than a million tons of
peanuts are produced per year [2], and about 25% of this
production corresponds to shells [3] which, in general, lack
value-added applications [4]. Some production industries
send their residues to others that burn them to obtain elec-
tricity [3]. Considering the low density of the peanut shells,
high volumes of this waste should be transported, increasing
the production costs of the legume.
Nowadays there are several researches seeking to valorize
biomass residues, looking forward to minimize their impact
on the environment and trying to obtain fuels or chemicals
from them. Diferent processes could be applied in order to
convert biomass, such as thermal, biological or mechanical
methods. Nevertheless, thermochemical processes seem to
be the most promising ways to transform these low value
bio-wastes considering their capacity to depolymerize most
of the organic compounds [1]. Besides, lower reaction times
are required for the reactions. Taking into account that pea-
nut shells are mainly composed of cellulose, hemicellulose
and lignin [5], from thermal options (combustion, pyrolysis,
gasifcation and liquefaction), pyrolysis seems to be the indi-
cated process for these rich in lignin materials. This process
consists in the thermal decomposition of the biopolymers
in absence of oxygen at 400–600 °C to yield char, oil and
gaseous products [6].
The liquid fraction of pyrolysis products, called bio-oil,
is a blend of organic molecules that could potentially be
used as fuel, additives or as fne chemicals source. One
major advantage is that the bio-oil is easier to transport than
the shells. Nevertheless, high oxygen compounds (such as
* Carla S. Fermanelli
cfermanelli@frc.utn.edu.ar
1
Centro de Investigación y Tecnología Química (CITeQ),
UTN – CONICET, Maestro Marcelo Lopez y Cruz Roja
Argentina, 5016 Córdoba, Argentina