ORGANOSOLV

Among various procedures known for isolation of lignin, use of organosolv

process for delignification of lignocellulosic materials allows safe and clean
pretreatment isolation processes of lignocellulosic feedstock. Since the lignin
obtained from this procedure is of high-quality due to absence of sulphur, free of
alkali/alkaline metals, soluble in organic solvent etc. it has attracted much
interest from researchers (Barta et al., 2014; Behling et al., 2016; Hussin et al.,
2014). Considering this aspect and understanding from literature that with a
change in substrate even if isolation procedure is kept constant variety of
depolymerization products can be obtained (Table 2), it was believed that a
methodical study is required to analyze the properties of isolated lignins derived
from diverse substrates using same isolation procedure. The study is important
from understanding that depending on local weather, soil condition, humidity,
temperature, growth time/period etc. along with age of plant, species etc.
typically lignin structures will vary and thus it becomes crucial to know even
smallest changes in lignin structures by employing advanced analytical tools.
Although, these issues are known but, in the literature there is a deficit of
detailed studies on this topic and thus it was decided to undertake detailed study
to understand the properties of lignin.
Considering this, in this study, focus was given on employing different
advanced analytical tools (ATR, 1D/2D HSQC NMR) for analyzing properties
(substructures, functional groups) of different lignins derived from same type of
crop waste species, rice husk (RH, Oryza sativa) by isolating the same using
organosolv technique. This work has extended into studies of the isolation as
well as physicochemical characterization of isolated organosolv lignins (ORGLs)
from lignocellulosic rice husks collected from different states of India (Karnataka,
Uttar Pradesh and West Bengal). Rice was used in this study since India produces
huge quantity of it with respect to world (2012: ca. 21.4%; 2013: ca. 20.7%;
2014: ca. 21.4%).
Dari jurnal:
Sandip K. S. and Paresh L. D., 2016, Isolation of lignin by organosolv process from
different varieties of rice husk: Understanding their physical and chemical
properties, Bioresource Technology. 221, 310317.
ACETOSOLV
Vegetable biomass has been for centuries a resource used by humanity
worldwide, for energy and cellulosic pulp production. Recently, biomass has lost
its value as an energy source based on the discovery of other sources more
profitable, and only the field of pulp and paper continued using large amounts of
lignocellulose. However, the production of paper pulp has traditionally been a
highly polluting process. The vast majority of paper pulp mills still use the Kraft
method, based on the action of a strongly alkaline solution of sulphur compounds
on vegetable fibers. Organosolv methods use organic compounds of relatively
low molecular weight as delignification agents, and are a good alternative to
Kraft due to the elimination of the sulphur compounds in cooking. The
researchers have achieved the delignification of plant tissues of all kinds using
representative agents of a wide sample of the organic functional groups:
alcohols, ketones, aldehydes, phenols, amines, amides, carboxylic acids (Lpez
et al., 2006; Rodrguez and Jimnez, 2008). Although lignin removal can be
achieved with high efficiency, in some cases, the physical properties of the paper
sheets from these pulps were lower compared to those of Kraft pulps. Therefore,
these pulps may be applied to the manufacture of special papers or obtaining
high purity cellulose, with a possible final destination as dissolving pulps (Sixta et
al., 2004; Vila et al., 2004), microcrystalline cellulose (Shansan et al., 2011),

microfibrillated cellulose (Serrano et al., 2011) or bioethanol (Requejo et al.,

2011), for example.
Some of organosolv processes may be performed at atmospheric pressure
and therefore at a low temperature, which results in a decreased severity of
treatment and, consequently, a reduced formation of degradation compounds
from sugars and lignin. This is of particular interest in the concept of the
biorefinery, reinvigorated in recent years and it pretends to use the main
components of the biomasses (Demirbas, 2009; Kamm and Kamm, 2004). Short
chain carboxylic acids are among the organics that can carry out the
fractionation. Acetic acid has been extensively investigated as delignification
and/or fractionation agent. Nimz et al. published the first works in the 80s on the
process named Acetosolv, who succeeded to pulp pine, spruce, and beech wood
(Nimz and Casten, 1986; Nimz et al., 1989). The Acetosolv process uses acetic
acid enriched (7090% by weight) aqueous mixtures with the addition of small
amounts of hydrochloric acid (typically 0.10.2% by weight) which contributes to
enhance the delignification through partial hydrolysis and solubilisation of
hemicelluloses and lignin. When pulping variables are appropriately chosen the
resulting pulps can show very low lignin content (Ligero et al., 2005) leaving a
solid residue with high cellulose content (Villaverde et al., 2010). Additionally,
acetosolv pulps could be easily bleached with TCF sequences including ozone,
hydrogen peroxide, oxygen, and peroxyacetic acid (Dapia et al., 2003; Vila et al.,
2004; Villaverde et al., 2011).
Oil palm empty fruit bunches (EFB) is a waste generated by the palm oil
industry after the separation of the fruits for oil extraction. This residue, which in
many countries, especially in Malaysia and Indonesia, is produced in very high
levels, is simply used as mulch, burnt for energy production or even burnt in the
plantations without any profit. Due to its high production and uniformity resulting
from the use of specific plant species EFB may not only be a waste but an
important resource for obtaining various high-value products through chemical
processing (Noor et al., 19982000). Shibata studied the chemical composition of
EFB, and other parts of the oil palm, finding very similar amounts of cellulose and
hemicelluloses and a lignin composed only by syringyl and guaiacyl units
(Shibata et al., 2008). EFB has been subjected to a number of treatments in
order to take advantage of this residue. An hydrothermal treatment was utilized
in order to obtain sugars and proved to enhance the enzymatic digestibility of
the solid residue (Shamsudin et al., 2012), which was studied by a mixture of
cellulase and b-1,4-glucosidase (Hamzah et al., 2011).
An acid-treatment removed 90% of the hemicelluloses and 32% of the
lignin, but left most of the cellulose, and a second alkali-treatment reached a
70% delignification yield (Kim et al., 2012). Different pulping methods were
applied to EFB. The effects of soda and soda-AQ pulping variables, even
reinforced with hydrogen peroxide, have been studied by means of factorial
experimental designs over yield, Kappa number, tensile and tear index (Wanrosli
et al., 2004) or Kappa number, pulp viscosity, brightness and a selectivity
measured as the ratio between the Kappa number reduction over the brightness
increase (Ng et al., 2011). Oxygen bleaching as the first stage of a bleaching
sequence was optimized for soda pulps obtained after a previous autohydrolysis
step (Leh et al., 2008) and a complete TCF bleaching sequence applied to sodaAQ pulps was also reported (Jimnez et al., 2009).
Among organosolv pulping methods EFB was subjected to pulping with
organic
solvents
with
a
high
boiling
temperature
(ethyleneglycol,
diethyleneglycol, ethanolamine and diethanolamine), showing the pulps from
amines to have better properties than the ones from glycols. (Rodrguez et al.,
2008b). Solvents with lower boiling point were also tested to treat EFB. Formic

acid (Ferrer et al., 2011b) and peroxyformic acid (Milox process) (Ferrer et al.,
2011a) treatments were simulated by means of polynomial and neural fuzzy
models. Their optimization predicted similar pulp properties values for both
processes, but a higher brightness in the Milox pulp, while liquor characteristics
diverged much more as no lignin could be precipitated from Milox liquor. To our
knowledge only one study on Acetosolv treatment of oil palm has been published
(Wanrosli et al., 2011) but applied to the leafy part (frond) of the tree. Therefore,
the aim of this work was to study the Acetosolv treatment of palm oil empty fruit
bunches by means of an experimental design factor, considering the influence of
the operational variables on the composition of the resulting pulp, with the aim
of finding the optimum conditions of operation to obtain a pulp for specialty
papers or other applications such as obtaining microcrystaline cellulose,
microfibrillated cellulose or bioethanol by simultaneous saccharification and
fermentation.
Dari jurnal:
Ferrer, A., Vega, A., Rodrguez, A. dan Jimnez, L., 2013, Acetosolv pulping for the
fractionation of empty fruit bunches from palm oil industry,Bioresource
Technology, 132, 115120.