Resources, Conservation & Recycling 143 (2019) 133–142

Contents lists available at ScienceDirect

Resources, Conservation & Recycling

journal homepage: www.elsevier.com/locate/resconrec

Full length article

Valorization of industrial paper waste by isolating cellulose nanostructures T

with different pretreatment methods
⁎
Alana Gabrieli de Souza, Daniel Belchior Rocha, Fabiany Sayuri Kano, Derval dos Santos Rosa
Laboratório de polímeros ambientalmente amigáveis, Universidade Federal do ABC – Santo André, Avenida dos Estados, 5001, CEP: 09210-580, SP, Brazil1

A R T I C LE I N FO A B S T R A C T

Keywords: Industrial paper wastes are an underestimated source of lignocellulosic materials. In this work cellulose na-
Cellulose nanostructures nostructures (CNS) were produced from this residue by acid hydrolysis and two chemical pretreatments con-
Industrial paper wastes sisting of an alkaline (CNS-I) or an acid (CNS-II) treatment. These pretreatments and the obtained CNSs were
Pretreatment influence characterized using compositional analysis, Fourier-transform infrared spectroscopy (FTIR), thermogravimetric
Controlled acid hydrolysis
analysis (TGA), scanning electron microscopy (SEM), dynamic light scattering (DLS), zeta potential, atomic force
Morphology
microscopy (AFM), and X-ray diffraction (XRD). Results reveal a reduction in the non-cellulosic compounds in
pre-treated samples, with different levels of components removal and lower lignin values for alkali treatment.
TGA reveals that CNSs present lower thermal stability than the residue. The SEM images revealed that pre-
treatment led to fiber breakage. The XDR diffractions show the co-existence of cellulose I and cellulose II, with
different crystallinity index for CNSs. The DLS and AFM revealed that the production of spherical nanoparticles
was following the dimensions of ˜195 for CNS-I and ˜350 nm for CNS-II. All the analysis allowed a more com-
prehensive understanding of the CNS properties and their possible applications. Finally, it is possible to conclude
that the conversion of paper wastes into CNS is an excellent opportunity to recovery this residue and aggregate
value to them.

1. Introduction quantities of generated residues, promoting the reuse and recycling of

Recently, the demand for sustainable and green materials has
prompted the development of new materials using industrial residues as
raw material (Feng et al., 2015; Satari and Karimi, 2018). The paper
industry is a major consumer of natural resources (e.g., wood and
water) and energy and results in high emissions of pollutants into the
environment (Bousios and Worrell, 2017; Corcelli et al., 2018; Jaria
et al., 2017; Thompson et al., 2001). These industrial residues result
from the mechanical and chemical process necessary to transform wood
fiber into cellulose pulp (Mastrantonio et al., 2015). The process results
in lignocellulosic residue with a significant amount of cellulose
wrapped by high amounts of hemicellulose and lignin (Mendes et al.,
2016).
Furthermore, the process also results in emissions containing heavy
metals, but at levels accepted by legislation. The pollutants are partially
dissolved in the residue during the paper production and are generally
burned with the final waste (Chen et al., 2016a; Thompson et al., 2001).
Various management strategies have been studied to minimize the high
these materials (Bayard et al., 2017).
Research focusing on cellulosic waste has expanded quickly within
the last decade. Agricultural residues such as rice husks (Johar et al.,
2012), eucalyptus fiber (Domingues et al., 2016), banana rachis
(Hernandez and Rosa, 2016), cotton fibers (Sun et al., 2016) and algae
marine biomass (Chen et al., 2016b) have been studied as sources for
the production of nanocellulose fibers and crystals. Also, industrial
residues have been studied, such as the coffee industry by-products and
tobacco wastes (Janissen and Huynh, 2018; Tuzzin et al., 2016). Cel-
lulose nanostructures (CNSs) are good options in the development of
nanocomposites because of their high crystallinity and large superficial
area, essential properties for high-performance composites (Johar et al.,
2012).
CNSs are typically produced from sources with a significative con-
tent of cellulose and small contents of other lignocellulosic compounds,
such as hemicellulose and lignin. These components are chemically
complex and highly resistant to the isolation of cellulose. The removal
of these lignocellulosic compounds through chemical pre-treatments

⁎
Corresponding author.
E-mail addresses: alana.gabrieli@ufabc.edu.br (A.G.d. Souza), daniel.rocha@ufabc.edu.br (D.B. Rocha), fkano@aluno.ufabc.edu.br (F.S. Kano),
derval.rosa@ufabc.edu.br (D.d.S. Rosa).
1
www.ufabc.edu.br

https://doi.org/10.1016/j.resconrec.2018.12.031
Received 14 September 2018; Received in revised form 26 December 2018; Accepted 27 December 2018
0921-3449/ © 2018 Published by Elsevier B.V.
A.G.d. Souza et al.
results in greater efficiency in the isolation processes. Therefore, pre-
treatment is needed to increase the hydrolysis efficiency (Mohapatra
et al., 2017). Different methods have been investigated for delignifi-
cation of the cellulosic wastes using alkalis, acids, high-pressure steam
explosion, and others (Li et al., 2017). The most common pretreatment
process is the aal method, which makes use of different concentrations
of sodium hydroxide (e.g., 2, 4, 10, 20 and 30 wt%) (Chen et al., 2016a;
Sisti et al., 2016; Yue et al., 2015). This method possesses advantages
such as high lignin solubilization and limited formation of inhibitors via
fermentation. The removal mechanism involves the saponification of
intermolecular ester bonds between the hemicellulose and lignin (Lee
et al., 2014). However, other studies have used diluted acid solutions to
remove lignocellulosic compounds. The most common acid pretreat-
ment are aqueous solutions of sulfuric and phosphoric acid. The ad-
vantages of these methods include higher reaction rates and increased
accessibility of cellulose (Lee et al., 2014). These pretreatments are a
process to break the compact structure of lignocellulosic residues.
Bleaching pretreatments are conducted to ensure the breaking of lignin
(Pérez et al., 2002). Oxidative delignification is the most common
process, and this method uses peracetic acid or hydrogen peroxide and
sodium hydroxide, which are efficient at removing lignin and in-
creasing biomass digestibility (Lee et al., 2014).
The production of CNSs via acid hydrolysis is the most common
process (Mascheroni et al., 2016). Acid hydrolysis typically uses sul-
furic, hydrochloric, or phosphoric acid to remove less-stable structures
(e.g., the amorphous region of cellulose and the hemicellulose) after the
lignin is removed. This process reduces the size and molar mass of the
cellulose, enabling the formation of 100–500 nm nanocrystals (Brinchi
et al., 2013). An extensive array of approaches (Table 1) has been
considered intending to decreasing the process severity of nanocellulose
isolation and enhancing the yield/reaction efficiency. Besides that,
there are other few methods to obtain nanostructures from different
materials, study their properties and ensure their stability.
The methods described here are well developed and can be applied
to raw materials in their natural state. However, industrial wastes are
subject to harsh chemical processes and contain different residues in its
composition. For paper residues, most of the cellulose has already been
removed to produce the cellulose pulp. This situation leads to a material
with high hemicellulose and lignin content and creates a challenge in
defining a method to isolate the cellulose. Only a few studies have fo-
cused on isolating CNSs from industrial wastes such as tobacco wastes
(Tuzzin et al., 2016) and waste cotton fabrics (Xiong et al., 2012).
The conversion of waste materials into valued products reduces the
environmental impacts of papermaking and adds value to the produc-
tion chain. This study investigates isolation of CNS from an inexpensive
and underused raw material – paper residue. Also, the efficiency of two
different pretreatments (alkali and acidic, in concentrations well es-
tablished in the literature) on the removal of the lignocellulosic com-
pound from this industrial residue and pretreatments effect in the
properties of the obtained CNSs by acid hydrolysis were evaluated.
Table 1
Different approaches for CNSs production.
Source Form Obtention Method
Arecanut husk fiber CNF Homogenization
Red algae marine biomass CNC H2SO4 hydrolysis
Sugarcane bagasse CNC H2SO4 hydrolysis
CNF Ball Milling
Sago (Cycas circinalis) seed shells CNC H2SO4 hydrolysis
Tobacco stems CNF Supermass colloider
wheat straw and kenaf fibers CNF Ball Milling
Amorpha fruticosa Linn CNF High-pressure homogenization
Fluff cellulose pulp CNF Dry grinding
Medium density fiberboards CNC H2SO4 hydrolysis
Garlic straw CNC H2SO4 hydrolysis
Sawdust wastes CNC HCl hydrolysis and homogenization
134
Resources, Conservation & Recycling 143 (2019) 133–142
Commercial nanocellulose was used as a reference for comparison. This
work also presents an alternative to the revalorization of the industrial
paper wastes using the final sludge of paper production to isolate CNSs.
2. Materials and methods
2.1. Materials
The paper residue (ETE sludge – according to the test report) used
was kindly donated by Multiverde Papeis Especiais Ltda Company
(Mogi das Cruzes, SP, Brazil) (pH 9.33, solid content 24.3 wt%). Acetic
acid (glacial, 99.85%), sulfuric acid (96%), hydrogen peroxide (34%)
and sodium hydroxide (99.85%) were obtained from Sigma-Aldrich
(Sao Paulo, Brazil).
2.2. Methods for the production of cellulose nanostructures
The cellulose nanostructures (CNSs) were obtained through two
different pretreatments. First, the paper residue (PR) was treated using
two different methodologies, an alkali (methodology I) and an acid
(methodology II), as described below. The methods chosen for this work
were applied after a study of different parameters present in the lit-
erature. Also, several tests were conducted to select the better condi-
tions, aiming at lower reagent, energy and time expenditure, and en-
suring a similar result to the conditions already reported in other
studies. The selected parameters are present below.
Methodology I: the alkali pretreatment was done adding the residue
into a alkaline aqueous solution of 2% wt/v sodium hydroxide solution,
in the ratio 1:20 (residue (g): solution (ml)), at 50 °C for 1 h. Then, the
residue was washed to neutral pH, filtered and dried for 4 h in an oven
with air circulation at 100 °C (sample PR-TI) (Berglund et al., 2016; Lee
et al., 2014; Pinheiro et al., 2017; Yue et al., 2015).
Methodology II: the acid pretreatment was done adding the residue
into an aqueous acid solution 92% v/v CH3COOH and 1.4% v/v H2SO4,
in the ratio 1:20 (residue (g): solution (ml)), at 80 °C for 3 h. Then, the
residue was washed to neutral pH, filtered and dried for 3 h in an oven
with air circulation at 50 °C (sample PR-TII) (Achaby et al., 2018; Lee
et al., 2014; Reddy et al., 2009; Souza et al., 2017).
After the respective pretreatments, bleaching was done for both
methodologies, submitting the pre-treated residues in 34% v/v H2O2
and 4% wt/v NaOH solution, during 1 h at 50 °C (Ferreira et al., 2018;
Owolabi et al., 2016). The samples were washed until neutral pH, fil-
tered and dried during 2 h at 80 °C. The bleached sample from PR-TI
was called PR-BI, and from PR-TII was called PR-BII.
The methodology of acid hydrolysis was adopted because already a
method used by industrial producers, and that can be applied in large
scale. As reported by Reid et al., 2017, laboratory production leads to
the same results that industrial production (Reid et al., 2017). The acid
hydrolysis was done with 40% v/v aqueous H2SO4 solution for 50 °C
and 1 h, and the methodology was similar that the use by USDA Forest
Average size (nm) Yield (w %) Reference
3–5 26 (Chandra et al., 2016)
22 52 (Chen et al., 2016b)
30 – (Sofla et al., 2016)
50
50 – (Naduparambath et al., 2018)
40 50 (Tuzzin et al., 2016)
30 66 (Nuruddin et al., 2016)
10 – (Zhuo et al., 2017)
118 67 (Lee and Mani, 2017)
17 27 (Gu et al., 2017)
500 20 (Kallel et al., 2016)
100 – (Kalita et al., 2015)
A.G.d. Souza et al. Resources, Conservation & Recycling 143 (2019) 133–142

Products Lab (Houtman, 2016; Reid et al., 2017), where are used re-
actors with 10 kg/day capacity. The solution was centrifuged at 6000
RPM during ten minutes and neutralized in a dialysis membrane for five
days. The hydrolyzed sample from PR-BI was called CNS-I, and from
PR-BII was called CNS-II.
The commercial nanocellulose (CNS-C) provided by Suzano Papel e
Celulose S.A. (Suzano, Brazil) (cellulose nanocrystals) was used to
compare a commercial product with CNS-I and CNS-II.
2.3. Characterization of the cellulose nanostructures
The percentage composition of extractives and lignin was de-
termined by compositional analysis using an adapted method based on
the neutral detergent fiber proposed by Van Soest (Van Soest et al.,
1991) of neutral and acid detergent and the TAPPI T 222om-22 (2002c)
methodology.
Fourier transform infrared spectroscopy (FTIR) was conducted using
a Frontier 94,942 (PerkinElmer, USA) in the range from 400 to
4000 cm−1 with 64 scans and a resolution of 4 cm−1. It was used an
attenuated total reflectance accessory.
The morphology of the samples was analyzed by scanning electron
microscopy (SEM). After the samples were prepared and dried in an
oven, as described in the experimental procedure, a little amount of the
dry powder of the samples was deposited with a spatula on carbon tape,
in an aluminum stub. The analyzed samples were: PR, PR-TI, PR-TII,
PR-BI, and PR-BII. Subsequently, each sample was sputter-coated with
gold. The samples were scanned in a JEOL - JCM 6010, operating with
an accelerating voltage of 5 KV. The Energy dispersive x-ray spectro-
scopy (EDS) spectra were obtained in the same equipment with samples
without gold coating.
The size of the nanoparticles (cellulose nanostructures (CNSs)) was
measured by the dynamic light scattering technique (DLS) (ALV-CGS3),
with 90° fixed scattering angle. A HeNe polarized laser (22 mW) with a
wavelength of 633 nm was used. Zeta potential values of the CNSs were
measured using a zeta potential analyzer (Malvern Instruments). The
suspensions were diluted to a concentration of 0.01 wt%.
Atomic force microscopy (AFM) experiments were performed in a
tapping mode in air using an AFM/SPM from Agilent, model 5500, at
room temperature and contact operating mode. For images examina-
tion, a droplet of the aqueous suspension (1 wt% of CNS) was added
onto a cleaned silicon wafer and then airdried during 6 h, at room
temperature. The scan was done at a rate of 0.5 Hz, with an image re-
solution of 256 × 256 pixels, with a silicon cantilever (nanosensor) of
constant force between 25 and 75 N.m−1 and resonance frequency of
120 kHz.
Thermogravimetric analysis (TGA) was carried out using STA 6000
instrument (PerkinElmer, USA). The samples were heated from 20 to
600 °C with a heating rate of 20 °C/min under a nitrogen flow.
XRD results are presented in the Appendices. This analysis shows
the crystalline structure of the residue and its nanostructures.
3. Results and discussion
3.1. Compositional analysis
The chemical composition of the paper waste and pre-treated
samples are listed in Table 2. Based on the presented results, the in-
dustrial treatments have a significant effect on the chemical composi-
tion of these samples. The PR sample had a lower percentage of cellu-
lose (34.3%) and higher percentages of hemicellulose (23.3%) and
lignin (19.3%) compared to that of chemically treated samples. These
values are similar to the lignocellulosic composition of softwood, the
feedstock for pulp production, whose lignin composition is between 20
and 35 wt% (Hildebrandt et al., 2019; Lee et al., 2014).
When applied the methodology I, the content of hemicellulose and
lignin decreased 22.7% and 35.2% respectively. When applied the
methodology II, the contents of hemicellulose and lignin decreased
14.8% and 17.1%, respectively. So, it is possible to observe that the
methodology I was more efficient in the non-cellulosic components.
There is an enrichment of cellulose content because treatments partially
remove the non-cellulosic components from the surface of the samples
(Chandra et al., 2016; Li et al., 2014).
After the bleaching steps, lignin and hemicellulose were sig-
nificantly reduced, which resulted in enriched cellulose fibers con-
siderably. Although the samples show good results after the treatments,
the found contents are still above the ideal level described in the lit-
erature (i.e., between 1 and 3%) (Delgado-Aguilar et al., 2016). Con-
sidering that the paper residue contains high concentrations of im-
purities, the obtained result is positive, in this case, that aims at
recycling of this previously discarded material. The above observations
indicate that the chemical treatments (alkali and acidic pretreatments
followed by bleaching) can damage the lignocellulosic structure, lead to
the cleavage of hemicellulose-lignin bonds and result into the removal
of lignin (Li et al., 2014).
The methodology I was more efficient at removing lignocellulosic
components from industrial paper residues. However, both methodol-
ogies demonstrated a more significant decrease in hemicellulose and
lignin compared with paper residue. Residual lignin can be a barrier
that reduces the effectiveness of the acid on the hydrolysis. Removal of
lignin could be improved by repeating the process or changing the
temperature and time parameters to remove the remaining lignin
(Delgado-Aguilar et al., 2016).
All of the samples presented significant ash in their composition,
which was expected considering the harsh chemical process involved to
obtain cellulose pulp (Lynn et al., 2018; Thompson et al., 2001). The
high ash concentration occurs due to the high concentration of che-
micals such as aluminum oxide, sodium hydroxide, titanium oxide and
silicon oxide (Frías et al., 2015).
3.2. Fourier transform infrared spectroscopy
The FT-IR spectra allow us to evaluate the presence of lignocellulose
compounds functional groups and draw a correlation with composi-
tional analysis. The spectra of the PR, PR-TI, and PR-TII is presented in
Fig. 1(a), and the spectra of the PR, PR-BI, and PR-BII is presented in
Fig. 1(b). The chemically treated samples exhibit mutual spectral bands

Table 2
The chemical composition of the samples at each stage of treatment.
Sample Extractives (%) Hemicellulose (%) Insoluble Lignin (%) Soluble Lignin (%) Cellulose (%) Ashes and Residues (%)

PR 4.5 ± 0.5 20.3 ± 0.8 17.7 ± 2.8 1.6 ± 0.4 34.3 ± 4.8 21.6 ± 0.5
PR-TI 3.7 ± 0.3 15.7 ± 0.3 12.0 ± 3.4 0.5 ± 0.2 56.4 ± 5.3 11.7 ± 2.3
PR-TII 3.7 ± 0.6 17.3 ± 0.8 15.4 ± 3.3 0.6 ± 0.2 43.5 ± 6.1 19.5 ± 1.5
PR-BI 2.4 ± .0.1 11.7 ± 0.5 4.4 ± 3.2 0.1 ± 0.1 69.9 ± 4.3 11.5 ± 2.1
PR-BII 1.4 ± 0.4 12.1 ± 0.2 7.6 ± 3.8 0.3 ± 0.1 64.2 ± 5.6 18.4 ± 1.3
CNS-C 0.5 ± 0.1 12.8 ± 0.7 0.2 ± 0.1 – 85.0 ± 3.1 1.5 ± 0.9

135
A.G.d. Souza et al.
Fig. 1. The FT-IR spectrum of (a) PR, PR-TI, and PR-TII; (b) PR, PR-BI and PR-BII and (c) CNS-I, CNS-II, and CNS-C.
around 3340 and 1440 cm−1, that correspond to the stretching of −OH
groups and CH2 bending, respectively, which are associated with cel-
lulose, lignin and hemicellulose (Beltramino et al., 2016; Rosa et al.,
2010; Soni et al., 2015; Tang et al., 2013). It is possible to identify peaks
at 1250 and 1330 cm−1 corresponding to the lignin, and a peak at
1040 cm−1 corresponding to C–OeC stretching; these vibration bands
are correlated with the lignin structure, which is probably due the
presence of residual lignin after the bleaching process (Chirayil et al.,
2014; Soucy et al., 2016; Xu et al., 2013; Zuluaga et al., 2009). Also, the
peak at 1640 cm−1 in all samples is relative to absorbed water in the
structure of cellulose. According to the literature, this band is asso-
ciated with the bending modes of water molecule due to a strong in-
teraction between cellulose and water (Haafiz et al., 2014). The pre-
sence of residual lignin during the hydrolysis process shields the
cellulose, protecting the amorphous fraction and negatively influencing
the likelihood of obtaining CNSs.
In Fig. 1(c), the spectra of CNS-I, CNS-II, and CNS-C are presented.
The dominant peaks are at 1640 cm−1, 1120 cm−1, 1040 cm−1 and
910 cm−1 that corresponds to absorbed water, C–O stretching vibra-
tion, C–H rock vibrations and C–H deformation vibration of cellulose
(Li et al., 2012), indicating the presence of cellulose as a main com-
ponent in the CNSs (Haafiz et al., 2014; Rosa et al., 2010). There are
also peaks of residual lignin at 1250 and 1330 cm−1 — also, the small
peaks in the 950–700 cm−1 region that represent the glycosidic -C1-O-
C4- deformation of the β-glycosidic link in cellulose, confirming the
136
Resources, Conservation & Recycling 143 (2019) 133–142
presence of cellulose structures after the acid hydrolysis (Henrique
et al., 2013; Jiang and Hsieh, 2013). Meanwhile, all CNSs exhibits
broadband in the region of 3500-3200 cm−1 due to the free OeH
stretching vibration of hydroxyl groups in cellulose molecules (Cao
et al., 2012).
3.3. Scanning electron microscopy
The morphology of the fibers is believed to be affected by the
chemical treatments. Fig. 2(a) show the SEM images of the fibers at
different stages of processing. The PR seems uneven due to the presence
of binding materials like hemicellulose and lignin. These binding ma-
terials are removed, and thereby fibers get detached from the surface by
the pretreatments. The surface changes after the treatments I and II
indicate the removal of cementing materials, and the bleaching helps to
eliminate the lignin (Chandra et al., 2016; Haafiz et al., 2014). The
bleaching process results in saponification of the fibers, resulted by the
alkalinity of the solution; and the addition of hydrogen peroxide causes
an excess of groups OH− (Lee et al., 2014). After bleaching treatment,
fiber bundles become defibrillated (Chirayil et al., 2014). The sample
PR-BI exhibits smoother and uniform fibrils surface, confirming the
removal of non-cellulosic components. However, it was not observed to
PR-BII, which presented aggregated irregular shaped fibrils.
According to Frías et al. (2015), the paper sludge consists of two
fractions: the organic fraction (cellulose, lignin, and hemicellulose) and
A.G.d. Souza et al.
Fig. 2. a) representative scanning electron micrographs of PR, PR-TI, PR-TII, PR-BI, and PR-BII and b) chemical composition of the samples obtained by EDS analysis.
the inorganic fraction (kaolinite, quartz, and smaller proportion of
other constituents). The chemical composition obtained by the EDS
analysis of the samples is presented in Fig. 2(b) and shows the presence
of natural components of lignocellulosic compounds, with significant
content of carbon and oxygen. However, since this is a residue from
pulp production, there are present common elements of the industrial
bleaching process as titanium, aluminum and the silicon, derived from
their respective oxides (TiO2, Al2O3, and SiO2), which are the base
composition of ashes obtained in compositional analysis (Frías et al.,
2015; Segui et al., 2012; Yan and Sagoe-Crentsil, 2012). The samples
from methodology I present sodium from alkali treatment and
bleaching which is less present in methodology II, even after the
bleaching process. All samples showed higher oxygen contents, which
probably occurs due to the presence of the oxides used in the paper
industry on the wood treatments. Besides that, after each treatment,
there was an increase in the metallic element contents, which can be
justified by the removal of lignocellulosic components from the organic
fraction.
The different mechanisms for the treatments are represented in
Fig. 3. In treatment I, the alkaline solution acts via a saponification
process, breaking ester bounds present on the lignin and hemicellulose
linkages and inducing the formation of surface roughness. In treatment
II, the acid solution hydrolyzes the bonds between the lignocellulosic
compounds and results in the degradation of superficial compounds to
reach the internal fiber (Lee et al., 2014). The effectiveness of these
mechanisms has been confirmed based in the compositional analysis.
137
Resources, Conservation & Recycling 143 (2019) 133–142
3.4. Dynamic light scattering and zeta potential
The DLS analysis considers the CNSs as spheres moving with
Brownian motion (Mascheroni et al., 2016). By the measurement of the
diffusion coefficient of the nanostructures, it is possible to determine its
hydrodynamic radius (RH) (Brito et al., 2012). The size distribution of
the particles is shown in Fig. 4(a).
The particle size distribution is remarkably monodispersed and ex-
hibits a single sharp peak with sizes between 80 and 350 nm for CNS-I
and sizes between 187 and 1996 nm for CNS-II (Fig. 5(b)). The meth-
odology I yielded smaller particles than methodology II. Fig. 4(c) shows
a scheme that represents the morphology of the CNSs after acid hy-
drolysis, considering the effect of the different pretreatments in the
final shape. The methodology I produced smaller nanospheres and rod-
like structures; however, both methods result in nanostructures and
aggregates. The yield of CNSs obtained concerning the initial amount of
paper residue is around 31% and 24% for the CNS-I and CNS-II, re-
spectively. The smaller nanosizes of the CNS-I probably are due to the
higher access of the sulfuric acid to the interior of the fibers. These
results were described before (FTIR and SEM analyses), and the sample
PR-B1 has less lignin and hemicellulose in its composition, which makes
the cellulose fibrils are more accessible to the acid. It results in higher
efficiency in the scission of the cellulose structures and dissolution of
the amorphous phase of cellulose, which is between the crystalline
phases. The amorphous cellulose removal facilitates the separation of
the crystalline structures in nanocellulose (the changes in the crystal-
linity of these samples are showed in the Appendices).
A.G.d. Souza et al.
Fig. 3. Representation of mechanism of different treatments: alkaline and acid methodologies.
The use of DLS analysis presumes that the analyzed structure is a
spherical particle, which diverges from the majority of reports of CNS
production (Chandra et al., 2016; Oksman et al., 2011). However
spherical CNSs have been reported for industrial residues of cotton fi-
bers and potato residue (Lu et al., 2013; Xiong et al., 2012). Atomic
force microscopy analysis was conducted to confirm and support the
majority formation of spherical CNSs.
The stability of nanocellulose suspension reflects the tendency of
CNSs to agglomerate. This characteristic can be studied by zeta po-
tential. The nanoparticles with similar electric charges repel each other
by the Coulomb force and thus affect the agglomeration and electro-
static stability of the suspension (Yang et al., 2017). The zeta potential
value for the CNS-I, CNS-II and CSN-C was −26.9 ± 7.0 and
−20.0 ± 2.71, −25.6 ± 0.4, respectively. The negative value in-
dicates the presence of −OH groups on the cellulose surface
(Naduparambath et al., 2018; Yang et al., 2017). From the data pre-
sented it may be inferred that the colloidal dispersions were not very
stable (Jiang and Hsieh, 2015). The zeta values of CNS-I are more
harmful than CNS-II, which means that CNS-I is more stable. Both
samples presented a similar zeta value comparing with CNS-C. The
dispersion difference could be related to the possibility of entanglement
Fig. 4. a) Scattering intensity curves as a function of the hydrodynamic radius (RH), (b) particles size of CNS-I, CNS-II, and CNS-C and (c) representation of CNSs
obtained after the hydrolysis.
138
Resources, Conservation & Recycling 143 (2019) 133–142
and the presence of residual lignin at the surface of obtained cellulose
nanostructures. Lignin and hemicelluloses are not expected to be pre-
sented at the surface of the CNSs, however, as seen at compositional
analysis, there is a residual content of these materials, which is prob-
ably affecting the results (Tonoli et al., 2012). Thus, the SO3− groups
are not presented in high enough quantity to change the zeta potential
values, corroborating the EDS results (Yang et al., 2017).
3.5. Atomic force microscopy
The AFM topography images (Fig. 5(a), (b), (c) and (d)) confirm the
successful production of nanoparticles; individual nanoparticles and
aggregates were observed. The most abundant form of CNS was sphe-
rical (Fig. 5(a) and (b)). After treatment, individual crystals were ob-
tained showing a rod-like structure (Fig. 5(c) and (d)) (Haafiz et al.,
2014; Li et al., 2018; Nge et al., 2013; Xiong et al., 2012). The spheres
(Fig. 5(a) and (b)) could be formed due to the self-assembled short
cellulose rods via interfacial hydrogen bonds (Lu and Hsieh, 2010).
Also, the different forms of nanocrystals (spheres and rod-like struc-
tures) cannot be separated by the conventional methods of filtration
and centrifugation (Lu and Hsieh, 2010). The spheres diameters were
A.G.d. Souza et al. Resources, Conservation & Recycling 143 (2019) 133–142

Fig. 5. 5 μm × 5 μm AFM topographical images of (a) CNS-I and (b) CNS-II; 2 μm × 2 μm AFM topographical images of (c) CNS-I and (d) CNS-II; (e) CNS-I and (f)
CNS-II diameter histogram.

estimated, and the data are presented in Fig. 5(e) and (f). The average
sizes are 200 nm for CNS-I and 305 nm for CNS-II, which corresponds
well with the DLS results. These findings reveal that the different pre-
treatments result in differently sized nanospheres. The methodology I
yielded a smaller particle size.
3.6. Thermogravimetric analysis
The thermal stabilities of pre-treated, bleached and CNSs are pre-
sented in Fig. 6(a), (b) and (c), respectively. A first mass loss around
100 °C is observed for both samples, and it is attributed to the eva-
poration of surface water, humidity, and low molecular mass
compounds (Chandra et al., 2016). For the pre-treated samples
(Fig. 6(a)), the initial decomposition temperature was 310, 295 and
245 °C for the PR, PR-TI, and PR-TII, respectively. The PR sample
showed a higher T10% than the other samples due to the presence of the
non-cellulosic constituents that act as barriers to initiate its thermal
degradation (Sá et al., 2015). Besides that, it is possible to observe that,
after the pretreatments, the samples tend to absorb higher humidity,
which is verified by T10%. This behavior can be attributed to spaces left
vacant after the removal of hemicellulose and lignin. The open surfaces
created in the pre-treated samples helps to absorb humidity (Sofla et al.,
2016). Also, this thermal behavior is associated with the ashes and
residues presence. The decrease in the thermal stability of the PR-TI and

Fig. 6. Thermal curves obtained by TGA for (a) PR, PR-TI, and PR-TII; (b) PR, PR-BI, and PR-BII and (c) CNS-I, CNS-II, and CNS-C.

139
A.G.d. Souza et al.
PR-TII is due to the greater exposition of the cellulose fibers due to the
efficiency of the pretreatments and bleaching (Du et al., 2016; Feng
et al., 2015).
Fig. 6(c) shows the thermal behavior of the CNS-I, CNS-II, and CNS-
C. The thermal degradation of cellulose and its nanostructures is critical
to assess the performance of the material and its possible applications
(Santmartí and Lee, 2018). For this reason, thermal stability has been
extensively studied. In this study, the hydrolyzed samples exhibit a
lower T10% compared with the pre-treated samples. The observed va-
lues of the decomposition temperature are also lower than those of the
commercial nanocellulose, which is used as a comparison. The lower
degradation temperature could be due to the smaller particle dimen-
sions (as shown in Fig. 3), which leads to higher specific surface area
(Lu et al., 2013; Sofla et al., 2016; Soni et al., 2015). Also, smaller
particles result in many free end-chains where decomposition easily
occurs, which justifies the lower thermal stability of the CNSs com-
paring with the pre-treated and bleached samples. Furthermore, CNS-C
has higher thermal stability due to the residual lignin present on the
CNS-I and CNS-II (Rambabu et al., 2016).
The differences in the thermal behavior of the hydrolyzed samples
and the CNS-C can be attributed to different factors, such as the degree
of crystallinity, presence of impurities and the type of cellulose sample
(Santmartí and Lee, 2018). The difference in the first step of weight loss
can also be attributed to a possible difference in the humidity of the
CNS-C. However, the second step, the degradation, is a process linked to
the scission of glycosidic bonds, leading to a reduction in the degree of
polymerization of cellulose. After the thermal activation, the next step
is the pyrolysis. This process is dependent on the cellulose structure and
crystallinity, which can justify the difference between the hydrolyzed
and commercial samples (Peng et al., 2013). It occurs because the hy-
drolyzed samples have cellulose I and II in its composition, and also
some residues, which can act as a thermal catalyzer. Also, probably the
samples have a different degree of polymerization, which is influenced
by the acid hydrolysis conditions.
3.7. Practical implications
This work presents a nanotechnology applied in industrial residues,
and the developed material is based on three premises: (i) the resulting
nanocellulose must be prepared from large-scale methodologies (i.e.,
acid hydrolysis); (b) components must be available and abundant (such
as the paper waste); (c) cost, environmental impact, and scalability
must enable generalized use.
Concerning the acid hydrolysis, some aspects have been studied to
minimize the environmental and economic impacts. Some options are
the recycling of reagents, the use of reactors and pipes, which must be
highly resistant due to the extreme conditions of pH, temperature and/
or pressure required by the acid hydrolysis. Also, it is important a re-
cycling system of sulfuric acid to separate the acid of the digested su-
gars released during the reaction, which makes possible to produce
from 3 to 1000 kg/day of nanocellulose (Chauve and Bras, 2014).
The industries that produce CNS use cotton or softwood pulp as raw
material. Although these materials have high purity, properties like
crystallinity, thermal and dimensional stability, size and morphology
are similar to those presented in this work. Due to the extensive phy-
sicochemical characterizations carried out in this study, it is possible to
compare the developed nanostructures with those currently commer-
cialized (Reid et al., 2017).
CNS are very expensive until now. The industrial plants were built
because the cost of CNS was estimated reasonable for the marketplace.
However, it needs to be cheaper to be commercially viable. For this, the
current plants are constituted as a significant research laboratory that
understands and investigates the operational costs of a new process, to
identify and evaluate new methods and process parameters, as well as
new equipment for the production line. As anticipated by some players
in the field, CNSs will be sold "at just several dollars a kilogram within a
140
Resources, Conservation & Recycling 143 (2019) 133–142
couple of years," which sounds, for now, a bit optimistic (Chauve and
Bras, 2014; Reid et al., 2017). Nowadays, 1 pound (˜11.8 solids) can be
purchased for $250 (Maine, 2018).
Therefore, the developed CNSs have the great potential to be used as
reinforcement for the manufacture of high-performance nanocompo-
sites, considering the thermal stability, dimensions, and morphology.
Thus, this work demonstrates a method that can be applied in large-
scale reactors, considering the adopted methodology, making the paper
waste commercially attractive. Overall, this study shows a scenario that
can minimize the pulp consumption by the substitution of this raw
material to the CNS obtention by the paper residue and optimize the
capital investment by the high add value of this new subproduct. Some
studies such as the life cycle assessment of this material could be con-
ducted to identify the potential risks associated with nanomaterials
productions, and to estimate environmental impacts from this process
in lab scale, pilot scale and industrial scale.
4. Conclusions
The present work showed that the cellulose nanostructures (CNSs)
could be successfully isolated from an abundant and low-cost residual
source, paper residue, by acid hydrolysis. Before the isolation process,
treatments with sodium hydroxide or acetic acid removed the non-
cellulosic constituents resulting in fibers with high cellulose content.
The alkaline treatment showed higher efficiency on the lignocellulosic
compounds removal and yielded better results than acidic treatment, as
it was confirmed via compositional analysis and FTIR concerning lig-
nocellulosic contents. So, the alkaline treatment was considered more
appropriate for CNSs isolation. After the treatments, CNSs were iso-
lated, and various characterizations showed the differences in the na-
nocellulose obtained from the pretreatments. CNSs revealed a reduction
in thermal stability. The nanocellulose present a combination of crys-
talline structures with cellulose I and cellulose II, with values of crys-
tallinity index for CNS-I, 75.9 and 68.6, and CNS-II, 66.9 and 57.6,
respectively (Appendices). The nanostructures presented spherical
structures with average sizes varying according to the methodology:
195 nm for the alkaline method and 340 nm for the acid method, and
the yield was 31% and 24%, respectively; AFM and DLS analyses con-
firmed these results. A possible correlation between the pretreatments
and particles shape could be observed due to the residual lignin.
Comparing with the commercial CNS, the samples of this study showed
excellent thermal stability, size distribution, and similar FTIR peaks.
Acknowledgments
The authors thank the UFABC and the Multiuser Central Facilities
(UFABC) for the experimental support. This work was supported by
CNPq (grant numbers 447180/2014-2, 163593/2015-9).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.resconrec.2018.12.
031.
References
Achaby, M.E., Kassab, Z., Barakat, A., Aboulkas, A., 2018. Alfa fibers as a viable, sus-
tainable source for cellulose nanocrystals extraction: application for improving the
tensile properties of biopolymer nanocomposite films. Ind. Crop. Prod. 112, 499–510.
https://doi.org/10.1016/j.indcrop.2017.12.049.
Bayard, R., Benbelkacem, H., Gourdon, R., Buffière, P., 2017. Characterization of selected
municipal solid waste components to estimate their biodegradability. J. Environ.
Manage. https://doi.org/10.1016/j.jenvman.2017.04.087.
Beltramino, F., Roncero, M.B., Torres, A.L., Vidal, T., Valls, C., 2016. Optimization of
sulfuric acid hydrolysis conditions for preparation of nanocrystalline cellulose from
enzymatically pretreated fibers. Cellulose 23, 1777–1789. https://doi.org/10.1007/
s10570-016-0897-y.
A.G.d. Souza et al.
Berglund, L., Noël, M., Aitomäki, Y., Öman, T., Oksman, K., 2016. Production potential of
cellulose nanofibers from industrial residues: efficiency and nanofiber characteristics.
Ind. Crops Prod. 92, 84–92. https://doi.org/10.1016/j.indcrop.2016.08.003.
Bousios, S., Worrell, E., 2017. Towards a Multiple Input-Multiple Output paper mill:
opportunities for alternative raw materials and sidestream valorisation in the paper
and board industry. Resour. Conserv. Recycl. 125, 218–232. https://doi.org/10.
1016/j.resconrec.2017.06.020.
Brinchi, L., Cotana, F., Fortunati, E., Kenny, J.M., 2013. Production of nanocrystalline
cellulose from lignocellulosic biomass: technology and applications. Carbohydr.
Polym. 94, 154–169. https://doi.org/10.1016/j.carbpol.2013.01.033.
Brito, B.S.L., Pereira, F.V., Putaux, J.L., Jean, B., 2012. Preparation, morphology and
structure of cellulose nanocrystals from bamboo fibers. Cellulose 19, 1527–1536.
https://doi.org/10.1007/s10570-012-9738-9.
Cao, X., Ding, B., Yu, J., Al-Deyab, S.S., 2012. Cellulose nanowhiskers extracted from
TEMPO-oxidized jute fibers. Carbohydr. Polym. 90, 1075–1080. https://doi.org/10.
1016/j.carbpol.2012.06.046.
Chandra, J.C., George, N., Narayanankutty, S.K., 2016. Isolation and characterization of
cellulose nanofibrils from arecanut husk fibre. Carbohydr. Polym. 142, 158–166.
https://doi.org/10.1016/j.carbpol.2016.01.015.
Chauve, G., Bras, J., 2014. Industrial Point of View of Nanocellulose Materials and Their
Possible Applications. [WWW Document]. https://doi.org/10.1142/
9789814566469 0014. https://umaine.edu/pdc/cellulose-nanomaterials/order-
nanocellulose/.
Chen, N., Zhu, J.Y., Tong, Z., 2016a. Fabrication of microfibrillated cellulose gel from
waste pulp sludge via mild maceration combined with mechanical shearing. Cellulose
23, 2573–2583. https://doi.org/10.1007/s10570-016-0959-1.
Chen, Y.W., Lee, H.V., Juan, J.C., Phang, S.M., 2016b. Production of new cellulose na-
nomaterial from red algae marine biomass Gelidium elegans. Carbohydr. Polym. 151,
1210–1219. https://doi.org/10.1016/j.carbpol.2016.06.083.
Chirayil, C.J., Joy, J., Mathew, L., Mozetic, M., Koetz, J., Thomas, S., 2014. Isolation and
characterization of cellulose nanofibrils from Helicteres isora plant. Ind. Crops Prod.
59, 27–34. https://doi.org/10.1016/j.indcrop.2014.04.020.
Corcelli, F., Ripa, M., Ulgiati, S., 2018. Efficiency and sustainability indicators for pa-
permaking from virgin pulp—an emergy-based case study. Resour. Conserv. Recycl.
131, 313–328. https://doi.org/10.1016/j.resconrec.2017.11.028.
Delgado-Aguilar, M., González, I., Tarrés, Q., Pèlach, M.À., Alcalà, M., Mutjé, P., 2016.
The key role of lignin in the production of low-cost lignocellulosic nanofibres for
papermaking applications. Ind. Crops Prod. 86, 295–300. https://doi.org/10.1016/j.
indcrop.2016.04.010.
Domingues, A.A., Pereira, F.V., Rita, M., Rojas, O.J., Petri, D.F.S., 2016. Interfacial
properties of cellulose nanoparticles obtained from acid and enzymatic hydrolysis of
cellulose. Cellulose. https://doi.org/10.1007/s10570-016-0965-3.
Du, H., Liu, C., Mu, X., Gong, W., Lv, D., Hong, Y., Si, C., Li, B., 2016. Preparation and
characterization of thermally stable cellulose nanocrystals via a sustainable approach
of FeCl3-catalyzed formic acid hydrolysis. Cellulose 23, 2389–2407. https://doi.org/
10.1007/s10570-016-0963-5.
Feng, X., Meng, X., Zhao, J., Miao, M., Shi, L., Zhang, S., Fang, J., 2015. Extraction and
preparation of cellulose nanocrystals from dealginate kelp residue: structures and
morphological characterization. Cellulose 22, 1763–1772. https://doi.org/10.1007/
s10570-015-0617-z.
Ferreira, F.V., Mariano, M., Rabelo, S.C., Gouveia, R.F., Lona, L.M.F., 2018. Isolation and
surface modification of cellulose nanocrystals from sugarcane bagasse waste: from a
micro- to a nano-scale view. Appl. Surf. Sci. 436, 1113–1122. https://doi.org/10.
1016/j.apsusc.2017.12.137.
Frías, M., Rodríguez, O., Sánchez De Rojas, M.I., 2015. Paper sludge, an environmentally
sound alternative source of MK-based cementitious materials. A review. Constr.
Build. Mater. 74, 37–48. https://doi.org/10.1016/j.conbuildmat.2014.10.007.
Gu, J., Hu, C., Zhong, R., Tu, D., Yun, H., Zhang, W., Leu, S.-Y., 2017. Isolation of cel-
lulose nanocrystals from medium density fiberboards. Carbohydr. Polym. 167, 70–78.
https://doi.org/10.1016/j.carbpol.2017.02.110.
Haafiz, M.K.M., Hassan, A., Zakaria, Z., Inuwa, I.M., 2014. Isolation and characterization
of cellulose nanowhiskers from oil palm biomass microcrystalline cellulose.
Carbohydr. Polym. 103, 119–125. https://doi.org/10.1016/j.carbpol.2013.11.055.
Henrique, M.A., Silvério, H.A., Flauzino Neto, W.P., Pasquini, D., 2013. Valorization of an
agro-industrial waste, mango seed, by the extraction and characterization of its cel-
lulose nanocrystals. J. Environ. Manage. 121, 202–209. https://doi.org/10.1016/j.
jenvman.2013.02.054.
Hernandez, C.C., Rosa, D.S., 2016. Extraction of cellulose nanowhiskers : natural fibers
source, methodology and application. Polymer Science: Research Advances, Practical
Applications and Educational Aspects, 1st ed. Formatex Research Center.
Hildebrandt, J., Budzinski, M., Nitzsche, R., Weber, A., Krombholz, A., Thrän, D., Bezama,
A., 2019. Assessing the technical and environmental performance of wood-based
fiber laminates with lignin based phenolic resin systems. Resour. Conserv. Recycl.
141, 455–464. https://doi.org/10.1016/j.resconrec.2018.10.029.
Houtman, C., 2016. Technoeconomic analysis of commercial-scale CNC production.
TAPPI Nano.
Janissen, B., Huynh, T., 2018. Chemical composition and value-adding applications of
coffee industry by-products: a review. Resour. Conserv. Recycl. 128, 110–117.
https://doi.org/10.1016/j.resconrec.2017.10.001.
Jaria, G., Silva, C.P., Ferreira, C.I.A., Otero, M., Calisto, V., 2017. Sludge from paper mill
effluent treatment as raw material to produce carbon adsorbents: an alternative waste
management strategy. J. Environ. Manage. 188, 203–211. https://doi.org/10.1016/j.
jenvman.2016.12.004.
Jiang, F., Hsieh, Y.Lo, 2013. Chemically and mechanically isolated nanocellulose and
their self-assembled structures. Carbohydr. Polym. 95, 32–40. https://doi.org/10.
1016/j.carbpol.2013.02.022.
141
Resources, Conservation & Recycling 143 (2019) 133–142
Jiang, F., Hsieh, Y.Lo, 2015. Cellulose nanocrystal isolation from tomato peels and as-
sembled nanofibers. Carbohydr. Polym. 122, 60–68. https://doi.org/10.1016/j.
carbpol.2014.12.064.
Johar, N., Ahmad, I., Dufresne, A., 2012. Extraction, preparation and characterization of
cellulose fibres and nanocrystals from rice husk. Ind. Crops Prod. 37, 93–99. https://
doi.org/10.1016/j.indcrop.2011.12.016.
Kalita, E., Nath, B.K., Agan, F., More, V., Deb, P., 2015. Isolation and characterization of
crystalline, autofluorescent, cellulose nanocrystals from saw dust wastes. Ind. Crops
Prod. 65, 550–555. https://doi.org/10.1016/j.indcrop.2014.10.004.
Kallel, F., Bettaieb, F., Khiari, R., García, A., Bras, J., Chaabouni, S.E., 2016. Isolation and
structural characterization of cellulose nanocrystals extracted from garlic straw re-
sidues. Ind. Crops Prod. 87, 287–296. https://doi.org/10.1016/j.indcrop.2016.04.
060.
Lee, H., Mani, S., 2017. Mechanical pretreatment of cellulose pulp to produce cellulose
nanofibrils using a dry grinding method. Ind. Crops Prod. 104, 179–187. https://doi.
org/10.1016/j.indcrop.2017.04.044.
Lee, H.V., Hamid, S.B.A., Zain, S.K., 2014. Conversion of lignocellulosic biomass to na-
nocellulose: structure and chemical process. Transfus. Apher. Sci. 2014. https://doi.
org/10.1155/2014/631013.
Li, J., Wei, X., Wang, Q., Chen, J., Chang, G., Kong, L., Su, J., Liu, Y., 2012. Homogeneous
isolation of nanocellulose from sugarcane bagasse by high pressure homogenization.
Carbohydr. Polym. 90, 1609–1613. https://doi.org/10.1016/j.carbpol.2012.07.038.
Li, M., Wang, L., Li, D., Cheng, Y.-L., Adhikari, B., 2014. Preparation and characterization
of cellulose nanofibers from de-pectinated sugar beet pulp. Carbohydr. Polym. 102,
136–143. https://doi.org/10.1016/j.carbpol.2013.11.021.
Li, B., Ding, L., Xu, H., Mu, X., Wang, H., 2017. Multivariate data analysis applied in
alkali-based pretreatment of corn stover. Resour. Conserv. Recycl. 122, 307–318.
https://doi.org/10.1016/j.resconrec.2016.12.007.
Li, X., Li, J., Gong, J., Kuang, Y., Mo, L., Song, T., 2018. Cellulose nanocrystals (CNCs)
with different crystalline allomorph for oil in water Pickering emulsions. Carbohydr.
Polym. 183, 303–310. https://doi.org/10.1016/j.carbpol.2017.12.085.
Lu, P., Hsieh, Y.Lo, 2010. Preparation and properties of cellulose nanocrystals: rods,
spheres, and network. Carbohydr. Polym. 82, 329–336. https://doi.org/10.1016/j.
carbpol.2010.04.073.
Lu, H., Gui, Y., Zheng, L., Liu, X., 2013. Morphological, crystalline, thermal and physi-
cochemical properties of cellulose nanocrystals obtained from sweet potato residue.
Food Res. Int. J. 50, 121–128. https://doi.org/10.1016/j.foodres.2012.10.013.
Lynn, C.J., Dhir, R.K., Ghataora, G.S., 2018. Environmental impacts of sewage sludge ash
in construction: leaching assessment. Resour. Conserv. Recycl. 136, 306–314.
https://doi.org/10.1016/j.resconrec.2018.04.029.
Maine, The Process Development Center, 2018. Order Nanocellulose. [WWW Document]
https://umaine.edu/pdc/cellulose-nanomaterials/order-nanocellulose/ URL https://
umaine.edu/pdc/cellulose-nano-crystals/. .
Mascheroni, E., Rampazzo, R., Ortenzi, M.A., Piva, G., Bonetti, S., Piergiovanni, L., 2016.
Comparison of cellulose nanocrystals obtained by sulfuric acid hydrolysis and am-
monium persulfate, to be used as coating on flexible food-packaging materials.
Cellulose 23, 779–793. https://doi.org/10.1007/s10570-015-0853-2.
Mastrantonio, G., Battaioto, L., Jones, C., Coustet, M., Chandi, H., Yamul, D.K., 2015.
Chemical conversion of paper industry effluents into carboxymethylcellulose. Process
Saf. Environ. Prot. 94, 315–321. https://doi.org/10.1016/j.psep.2014.07.005.
Mendes, C.V.T., Cruz, C.H.G., Reis, D.F.N., Carvalho, M.G.V.S., Rocha, J.M.S., 2016.
Integrated bioconversion of pulp and paper primary sludge to second generation
bioethanol using Saccharomyces cerevisiae ATCC 26602. Bioresour. Technol. 220,
161–167. https://doi.org/10.1016/j.biortech.2016.07.140.
Mohapatra, S., Dandapat, S.J., Thatoi, H., 2017. Physicochemical characterization,
modelling and optimization of ultrasono-assisted acid pretreatment of two
Pennisetum sp. Using Taguchi and artificial neural networking for enhanced de-
lignification. J. Environ. Manage. 187, 537–549. https://doi.org/10.1016/j.jenvman.
2016.09.060.
Naduparambath, S., J, T.V., Shaniba, V., S, M.P., Balan, A.K., Purushothaman, E., 2018.
Isolation and characterisation of cellulose nanocrystals from sago seed shells.
Carbohydr. Polym. 180, 13–20. https://doi.org/10.1016/j.carbpol.2017.09.088.
Nge, T.T., Lee, S.H., Endo, T., 2013. Preparation of nanoscale cellulose materials with
different morphologies by mechanical treatments and their characterization.
Cellulose 20, 1841–1852. https://doi.org/10.1007/s10570-013-9962-y.
Nuruddin, M., Hosur, M., Uddin, M.J., Baah, D., Jeelani, S., 2016. A novel approach for
extracting cellulose nanofibers from lignocellulosic biomass by ball milling combined
with chemical treatment. J. Appl. Polym. Sci. 133. https://doi.org/10.1002/app.
42990.
Oksman, K., Etang, J.A., Mathew, A.P., Jonoobi, M., 2011. Cellulose nanowhiskers se-
parated from a bio-residue from wood bioethanol production. Biomass Bioenergy 35,
146–152. https://doi.org/10.1016/j.biombioe.2010.08.021.
Owolabi, A.F., Haafiz, M.K.M., Hossain, S., Hussin, M.H., Fazita, M.R.N., 2016. Influence
of alkaline hydrogen peroxide pre-hydrolysis on the isolation of microcrystalline
cellulose from oil palm fronds. Int. J. Biol. Macromol. https://doi.org/10.1016/j.
ijbiomac.2016.11.016.
Peng, Y., Gardner, D.J., Han, Y., Kiziltas, A., Cai, Z., Tshabalala, M.A., 2013. Influence of
drying method on the material properties of nanocellulose I: thermostability and
crystallinity. Cellulose 20, 2379–2392. https://doi.org/10.1007/s10570-013-0019-z.
Pérez, J., Muñoz-Dorado, J., De La Rubia, T., Martínez, J., 2002. Biodegradation and
biological treatments of cellulose, hemicellulose and lignin: an overview. Int.
Microbiol. 5, 53–63. https://doi.org/10.1007/s10123-002-0062-3.
Pinheiro, I.F., Ferreira, F.V., Souza, D.H.S., Gouveia, R.F., Lona, L.M.F., Morales, A.R.,
Mei, L.H.I., 2017. Mechanical, rheological and degradation properties of PBAT na-
nocomposites reinforced by functionalized cellulose nanocrystals. Eur. Polym. J. 97,
356–365. https://doi.org/10.1016/j.eurpolymj.2017.10.026.
A.G.d. Souza et al.
Rambabu, N., Panthapulakkal, S., Sain, M., Dalai, A.K., 2016. Production of nanocellulose
fibers from pinecone biomass: evaluation and optimization of chemical and me-
chanical treatment conditions on mechanical properties of nanocellulose films. Ind.
Crops Prod. 83, 746–754. https://doi.org/10.1016/j.indcrop.2015.11.083.
Reddy, K.O., Guduri, B.R., Rajulu, A.V., 2009. Structural characterization and tensile
properties of Borassus fruit fibers. J. Appl. Polym. Sci. 114, 603–611. https://doi.org/
10.1002/app.
Reid, M.S., Villalobos, M., Cranston, E.D., 2017. Benchmarking cellulose nanocrystals:
from the laboratory to industrial production. Langmuir 33, 1583–1598. https://doi.
org/10.1021/acs.langmuir.6b03765.
Rosa, M.F., Medeiros, E.S., Malmonge, J.A., Gregorski, K.S., Wood, D.F., Mattoso, L.H.C.,
Glenn, G., Orts, W.J., Imam, S.H., 2010. Cellulose nanowhiskers from coconut husk
fibers: effect of preparation conditions on their thermal and morphological behavior.
Carbohydr. Polym. 81, 83–92. https://doi.org/10.1016/j.carbpol.2010.01.059.
Sá, R.Mde, Miranda, C.Sde, José, N.M., 2015. Preparation and characterization of na-
nowhiskers cellulose from Fiber arrowroot (Maranta arundinacea). Mater. Res. 18,
225–229. https://doi.org/10.1590/1516-1439.366214.
Santmartí, A., Lee, Koon-Yang, 2018. Crystallinity and Thermal Stability of
Nanocellulose. Nanocellulose and Sustainability. pp. 68. https://doi.org/10.1002/
jhet.2254.
Satari, B., Karimi, K., 2018. Citrus processing wastes: environmental impacts, recent
advances, and future perspectives in total valorization. Resour. Conserv. Recycl. 129,
153–167. https://doi.org/10.1016/j.resconrec.2017.10.032.
Segui, P., Aubert, J.E., Husson, B., Measson, M., 2012. Characterization of wastepaper
sludge ash for its valorization as a component of hydraulic binders. Appl. Clay Sci. 57,
79–85. https://doi.org/10.1016/j.clay.2012.01.007.
Sisti, L., Totaro, G., Vannini, M., Fabbri, P., Kalia, S., Zatta, A., Celli, A., 2016. Evaluation
of the retting process as a pre-treatment of vegetable fibers for the preparation of
high-performance polymer biocomposites. Ind. Crops Prod. 81, 56–65. https://doi.
org/10.1016/j.indcrop.2015.11.045.
Sofla, M.R.K., Brown, R.J., Tsuzuki, T., Rainey, T.J., 2016. A comparison of cellulose
nanocrystals and cellulose nanofibres extracted from bagasse using acid and ball
milling methods. Adv. Nat. Sci. Nanosci. Nanotechnol. 7. https://doi.org/10.1088/
2043-6262/7/3/035004.
Soni, B., Hassan, E.B., Mahmoud, B., 2015. Chemical isolation and characterization of
different cellulose nanofibers from cotton stalks. Carbohydr. Polym. 134, 581–589.
https://doi.org/10.1016/j.carbpol.2015.08.031.
Soucy, J., Koubaa, A., Migneault, S., Riedl, B., 2016. Chemical composition and surface
properties of paper mill sludge and their impact on high density polyethylene (HDPE)
composites. J. Wood Chem. Technol. 36, 77–93. https://doi.org/10.1080/02773813.
2015.1057647.
Souza, A.G.De, Kano, F.S., Bonvent, J.J., Rosa, D.S., 2017. Cellulose nanostructures ob-
tained from waste paper industry: a comparison of acid and mechanical isolation
methods. Mater. Res. 1–6.
142
Resources, Conservation & Recycling 143 (2019) 133–142
Sun, B., Zhang, M., Hou, Q., Liu, R., Wu, T., Si, C., 2016. Further characterization of
cellulose nanocrystal (CNC) preparation from sulfuric acid hydrolysis of cotton fibers.
Cellulose 23, 439–450. https://doi.org/10.1007/s10570-015-0803-z.
Tang, L., Huang, B., Lu, Q., Wang, S., Ou, W., Lin, W., Chen, X., 2013. Ultrasonication-
assisted manufacture of cellulose nanocrystals esterified with acetic acid. Bioresour.
Technol. 127, 100–105. https://doi.org/10.1016/j.biortech.2012.09.133.
Thompson, G., Swain, J., Kay, M., Forster, C.F., 2001. The treatment of pulp and paper
mill effluent: a review. Bioresour. Technol. 77, 275–286. https://doi.org/10.1016/
S0960-8524(00)00060-2.
Tonoli, G.H.D., Teixeira, E.M., Corrêa, A.C., Marconcini, J.M., Caixeta, L.A., Pereira-Da-
Silva, M.A., Mattoso, L.H.C., 2012. Cellulose micro/nanofibres from Eucalyptus kraft
pulp: preparation and properties. Carbohydr. Polym. 89, 80–88. https://doi.org/10.
1016/j.carbpol.2012.02.052.
Tuzzin, G., Godinho, M., Dettmer, A., Zattera, A.J., 2016. Nanofibrillated cellulose from
tobacco industry wastes. Carbohydr. Polym. 148, 69–77. https://doi.org/10.1016/j.
carbpol.2016.04.045.
Van Soest, P.J., Robertson, J.B., Lewis, B.A., 1991. Methods for dietary Fiber, neutral
detergent Fiber, and nonstarch polysaccharides in relation to animal nutrition. J.
Dairy Sci. 74, 3583–3597. https://doi.org/10.3168/jds.S0022-0302(91)78551-2.
Xiong, R., Zhang, X., Tian, D., Zhou, Z., Lu, C., 2012. Comparing microcrystalline with
spherical nanocrystalline cellulose from waste cotton fabrics. Cellulose 19,
1189–1198. https://doi.org/10.1007/s10570-012-9730-4.
Xu, F., Yu, J., Tesso, T., Dowell, F., Wang, D., 2013. Qualitative and quantitative analysis
of lignocellulosic biomass using infrared techniques: a mini-review. Appl. Energy
104, 801–809. https://doi.org/10.1016/j.apenergy.2012.12.019.
Yan, S., Sagoe-Crentsil, K., 2012. Properties of wastepaper sludge in geopolymer mortars
for masonry applications. J. Environ. Manage. 112, 27–32. https://doi.org/10.1016/
j.jenvman.2012.07.008.
Yang, X., Han, F., Xu, C., Jiang, S., Huang, L., Liu, L., Xia, Z., 2017. Effects of preparation
methods on the morphology and properties of nanocellulose (NC) extracted from corn
husk. Ind. Crops Prod. 109, 241–247. https://doi.org/10.1016/j.indcrop.2017.08.
032.
Yue, Y., Han, J., Han, G., Aita, G.M., Wu, Q., 2015. Cellulose fibers isolated from en-
ergycane bagasse using alkaline and sodium chlorite treatments: structural, chemical
and thermal properties. Ind. Crops Prod. 76, 355–363. https://doi.org/10.1016/j.
indcrop.2015.07.006.
Zhuo, X., Liu, C., Pan, R., Dong, X., Li, Y., 2017. Nanocellulose mechanically isolated from
Amorpha fruticosa linn. ACS Sustain. Chem. Eng. 5, 4414–4420. https://doi.org/10.
1021/acssuschemeng.7b00478.
Zuluaga, R., Putaux, J.L., Cruz, J., Vélez, J., Mondragon, I., Gañán, P., 2009. Cellulose
microfibrils from banana rachis: effect of alkaline treatments on structural and
morphological features. Carbohydr. Polym. 76, 51–59. https://doi.org/10.1016/j.
carbpol.2008.09.024.