Professional Documents
Culture Documents
December 2014
Chemical Engineering Department, Instituto Superior Tcnico, Avenida Rovisco Pais, 1, 1049-001 Lisbon, Portugal.
Abstract
In the last decades, more attention has focused on lignocellulosic materials, for being sustainable
resources with high potential to create new value-added biomaterials. Among these resources main
highlight has been given to hemicelluloses, in particular xylans, since they have, together with their
derivatives, a wide range of applications in industry, namely, pulp, food, pharmaceutical and biofuels.
The main purpose of the present work was focused on alkaline extraction of bleached Kraft pulp of
Eucalyptus Globulus, and in the isolation of xylans present in alkaline extract, with high purity and yield. To
optimize the extractions, the effect of two parameters was evaluated, the stirring speed and the extraction
time. With the speed increase there was an increase in yield, however the second parameter does not
show any influence. The extraction yield, for the various tests, varied between 65 -85%.
The isolation of xylans was performed by two different methods: neutralization with dilute acid and
precipitation with alcohol (ethanol and methanol). Due to the presence of impurities in the precipitate, the
washing importance was studied by different ways. Water washing yielded samples with purity values up to
99%, while with methanol those values range from 36-84%. The characterization of xylan indicated that the
average molecular weights were 16.8 to 22.7 kDa and the xylan yields varied between 43 and 97%.
It was concluded that nitric acid is the solvent that yielded more pure xylan and the use of alcohol
requires the subsequent washing with water to neutralize the sample, resulting in low yields due to the
losses in wash process. It was also found that the alcohol content appears to influence the diversity of
molecular weights of precipitate.
Keywords: Eucalyptus globulus, Bleached Kraft pulp, Alkaline Extraction, Precipitation and Xylans.
sunflower hulls, wheat, rye and oat bran or sugarbeet
pulp (Srossy, Zsuzsa, 2011).
Portugal, a country with a large forest area, 38% of
the national territory, where the industrial sector of
pulp and paper contributes a lot to the Portuguese
economy, shows great potential to obtain xylans.
Eucalypt wood is the increasingly dominating source
of short fibers for the pulp and paper industry in our
country. Particularly, Eucalyptus globulus is the
dominant raw material, rich in hemicelluloses namely
xylan (about 16%) for bleached hardwood kraft pulp
production (Lisboa, S., et al., 2005; Shatalov, A., et
al., 1999).
The structural diversity and complexity of xylans are
shown to depend on the botanic source and are also
changed by the way they are extracted and purified.
Various suitable extraction procedures for the isolaton
of xylans from different plant sources are described in
1. Introduction
Considerable attention has been focused on
alternative and sustainable resources to produce fuels
and chemicals that are currently derived from fossil
oils.
One example of a promising biomaterial is xylan, a
hemicellulose largely found in nature, being
considered the second most abundant polysaccharide
after cellulose. They occur in close association with
cellulose and lignin in plant cell wall in lignified
tissues.
The most potential sources of xylans include forest
and pulping waste products from hardwoods and
softwoods and many agricultural crops such as straw,
sugar cane, corn stalks and cobs, hulls and husks
from starch production (Ebringerova & Heinze, 2000),
Pulp 1
Pulp 2
Ash (%)
0,139
0,194
Pentosans (%)
16,89
16,44
SR
64
66
Humidity (%)
58,0
70,6
2.1 Materials
2
2.8
2.6
Pentosan Analysis
2.7
Carbohydrate analysis
2.7.1
Acid Hydrolysis
2.7.2
HPAEC-PAD
2.7.3
Solubility of xylan
2.9
UV-H2SO4 Method
calibrated
with
pullulan
standard
Laboratories) in the range of 5,8-48 kDa.
2.10
(Polymer
2.11
2.12
Tests
2.13
Washed water analysis by Laboratrio
de Anlises of IST
In parallel with the previously method, some wash
water samples were analysed, by ion chromatography
at the Laboratrio de Anlises of IST, for ion
concentration determinations.
Pentosan content
Ash content
Pentosan content
Ash content
Yield of extraction
Tests
Stirring speed (rpm)
Tests
Tests
(%) =
(%) =
()
100
()
()
100
()
Yield of extraction
Tests
Ethanol
Acid/Filtrate (mL/mL)
AALF-acetic acid-liquid filtrate; AASO-acetic acid-supernatant; ASSOsulfuric acid-supernatant; H2O washed with water until pH=7; LMMethanol washing only (alkaline pp)
Methanol
AALF-acetic acid-liquid filtrate; AASO-acetic acid-supernatant; ASSOsulfuric acid-supernatant; H2O washed with water until pH=7; LMMethanol washing only (alkaline pp)
LMT-Washed with methanol; NL-Not washed; H2O-washed with water
(to remove salts);
samples
3.2.1 HPAEC-PAD
The hemicelluloses are a mixture of different
polysaccharides, in which the sugar composition can
vary depending on its source and method of isolation.
The sugar composition of hemicellulosic samples is
showed in Figure 14 for samples obtained by alkaline
filtrate neutralization with acid and in Figure 15 for
samples obtained by alkaline filtrate precipitation with
alcohol.
Fig.16 Xylose composition of xylan samples obtained
by alkaline filtrate neutralization with acid.
Ara-Arabinose;
Mannose
Gal-Galactose;
Glc-Glucose;
Xyl-Xylose;
Man-
RI
Xylans
Salt: LiCl
Mw
Mn
PD
HA LM
AA LM
SA H2O
ET50 H2O
NA H2O
PA H2O
MT30 ASSO
22715
21773
21233
18658
19938
16828
20326
14810
14339
14688
12317
13712
8690
13722
1,53
1,51
1,45
1,51
1,45
1,93
1,48
HA- neutralization w/ hydrocloric acid; AA- w/ acetic acid; SA-w/ sulfuric acid; NAw/ nitric acid; PA w/phosphoric acid; ET50-precipitation w/50%Ethanol; MT30
precipitation w/ 30%Methanol.
http://webbook.nist.gov/cgi/cbook.cgi?ID=B6000542&Units=
SI&Mask=80#IR-Spec
Conclusions
4. Acknowledgements
This work was supported by the grants from Prof. Dr.
Lurdes Serrano (Thesis coordinator - IST) and Prof.
Dr. Ana Paula Dias (IST) for the collaboration in FTIR
and thermogravimetric analysis, to RAIZ for the
collaboration in HPAEC analysis and pentosan
determination and to Aveiro University for the
collaboration in GPC analysis.
5. References
Albalasmeh, Ammar A., Berhe, Asmeret Asefaw,
Ghezzehei, Teamrat A. (2013). A new method for
rapid determination of carbohydrate and total carbon
concentrations
using
UV
spectrophotometry.
Carbohydrate Polymers, 97 (2), 253-261.
Deutschmann, Rudolf, Dekker, Robert F. H. (2012).
From plant biomass to bio-based chemicals: Latest
developments in xylan research. Biotechnology
Advances, 30, 1627-1640.
9
Peng. F., Bian, J., Jia, N., Peng, P., Sun, R. C., Liu, S.
J. (2012). Isolation and fractionation of hemicelluloses
from Salix Psammophila. Cellulose Chemistry and
Technology, 46 (3-4), 177-184.
Shatalov,
Anatoly
A.,
Pereira,
H.
(2002).
Carbohydrate behavior of Arundo donax L. in ethanolalkali medium of variable composition during
organosolv delignification. Carbohydrate Polymers,
49, 331336.
APPENDIX
Fig. A FTIR spectra of xylan obtained from alkaline filtrate by sulfuric acid neutralization and washed with methanol (LM blue
spectra), not washed (NL- green spectra), washed with water (H2O- red spectra) and standard xylan (black spectra).
Fig. B FTIR spectra of xylan obtained from alkaline filtrate ethanol precipitation (30% red spectra, 50%-blue spectra and
70%- green spectra, in solution), washed with water (H2O) and standard xylan (black spectra).
Fig. C TG-DTG curves of xylan obtained from alkaline filtrate by phosphoric acid neutralization and washed with methanol (PA
LMT green thermogram) and standard xylan (blue thermogram).
11