Journal of Cleaner Production 240 (2019) 118220

Contents lists available at ScienceDirect

Journal of Cleaner Production

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

Green liquor dregs and slaker grits residues characterization of a pulp

and paper mill for future application on ceramic products
^ nica Ribeiro dos Santos a, *, Marcelo Dezena Cabrelon b, Eliandra de Sousa Triche
Vero ^s a,
Eduardo Quinteiro a
a ~o Paulo e UNIFESP, Sa
Science and Technology Institute e ICT, Universidade Federal de Sa ~o Jos
e Dos Campos, SP, 12231-280, Brazil
b
Innovare Intelig^ ^mica LTDA, Sa
encia em Cera ~o Paulo, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Green liquor dregs and slaker grits are pulp and paper mill residues usually landfilled. Whit high calcium
Received 21 May 2019 carbonate content, its use as alternative raw materials in traditional ceramic products becomes an
Received in revised form interesting study field. In order to evaluate its incorporation potential, the residues characterization with
3 August 2019
diverse approaches was performed and for the first time reunited exploring this eco-friendly intent.
Accepted 28 August 2019
Available online 28 August 2019
Green liquor dregs and slaker grits were characterized by its chemical and mineralogical composition
(XRF, XRD, FT-IR); physical and morphological characteristics (particle size, BET surface area, density,
Handling editor: Jin-Kuk Kim SEM) and thermal properties (TGA). Chemical and mineralogical analysis reveals the high calcium car-
bonate content in calcite form especially on slaker grits, that has less inorganic and organic contaminants
Keywords: than green liquor dregs. Smaller irregular-shaped particles and bigger surface area was found on this last
Traditional ceramics residue, comparing with slaker grits. The thermal analysis indicated a lower calcite decomposition for
Solid residues green liquor dregs (720
C), while this event on slaker grits occurred 40
C above (760
C). Thus, it was
Waste management observed the residues behavior and characteristics are much alike calcium carbonate itself, especially
Green liquor dregs waste
slaker grits, considering its composition, morphology and thermal events. As conclusion, the potentiality
Slaker grits waste
uses of green liquor dregs and slaker grits as alternative raw materials on ceramic products was revealed.
Being able to incorporate clay, concrete, glasses and great majority of other ceramic products, these
residues use will generate excellent benefit-cost ratio to industries and environment.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction alternative raw materials. New proposes to waste management are

Pulp and paper mills generate organic and inorganic residues
that wide vary in their properties during the Kraft process, such as
green liquor dregs, slaker grits, biomass ash and lime sludge
(Martínez-Lage et al., 2016). It is documented that world paper
production reached 401 Mt in 2015, while the wastes production is
estimated to over 1 Mt per year (GEDF-CD/FIEP, 2016; Sim~ ao et al.,
2018). Usually landfilled, these residues are able to promote
expressive negative ecological impacts; soil contamination, leach-
ing of toxic compounds causing groundwater pollution and odor
emission (Saikia et al., 2007; Poykio et al., 2014). Furthermore,
these residues landfilling is a natural resources waste, once it has
reuse high potential on productive processes as high quality
* Corresponding author. 330 Talim Street e Vila Nair, S~  dos Campos, SP,
ao Jose
12231-280, Brazil.
E-mail address: veronica.ribeiro@unifesp.br (V. Ribeiro dos Santos).
needed to minimize landfill disposal and can also generates eco-
nomic and social gain (Sima ~o et al., 2018). The possibility of recy-
cling and reusing such wastes is currently a promising study field
that lacks of attention (M€ € et al., 2016) and in order to evaluate
akela
alternative uses complete understanding of its fundamentals
properties and origins is needed.
The Kraft process (Fig. 1) consist on the recovery of the active
chemical agents that dissolves lignin to liberate the cellulose fibers
from the wood matrix; sodium hydrate (NaOH) and sodium sulfate
(Na2S), white liquor major components (Manskinen et al., 2011;
Bajpai, 2015). Wood reacts with white liquor during cooking in a
digestor and cellulose is obtained and separated, resulting in a
black liquor rich in lignin and chemical agents of the white liquor
(Melo et al., 2011). With low solid content, black liquor is concen-
trated by evaporation and strong black liquor is obtained. The next
step consists on the smelt obtention by strong black liquor burning
in the recovery boiler. The smelt is composed of a mixture of

https://doi.org/10.1016/j.jclepro.2019.118220
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
2 V. Ribeiro dos Santos et al. / Journal of Cleaner Production 240 (2019) 118220
Fig. 1. Main steps of the chemical recovery process at Kraft pulp mills (Adapted from Sima
dissolved salts (sulfides, sulfates, carbonates and sodium and po-
tassium chlorides) that are majorly cooking inactive, being trans-
formed back into active substances by its dissolution, forming the
green liquor, followed by clarification and recausticizing by reaction
with calcium hydroxide (Ca(OH)2) obtained by hydration of calcium
oxide (CaO) (Melo et al., 2011; Kinnarinen et al., 2016; Martins et al.,
2007). The Kraft process results in high rates of chemicals recovery,
and the inorganic impurities that consists of non-process elements
and inert materials are removed of the cicle to prevent dificulties on
the mill operation, and are principally originated from inert CaCO3
on limestone, and oxides of metals such as iron, aluminum and
silicon (Kinnarinen et al., 2016; Andreola et al., 2011).
Among the generated wastes, green liquor dregs and slaker grits
have been recently studied as alternative products in agriculture
and construction field (Sima ~o et al., 2018). Due to its high alkalinity
and salts present, these residues are being used with great results
as fertilizers and soil amendments to prevent the acidification
(Ma €kela
€ et al., 2012). Na and K salts presents are easily soluble,
while Ca and Mg shows limited solubility but are source of calcium
for the plants (Mahmoudkhani et al., 2004; Almeida et al., 2007).
Although used in agriculture, green liquor dregs and slaker grits
contain heavy metals environmental hazardous, such as Cd, Cu and
Zn, but in concentrations that allow its use as forest fertilizers
€
(Manskinen et al., 2011; Osterås et al., 2005). Reports about these
elements’ separation are now being studied (Golmae et al., 2018).
Slaker grits has much lower heavy metals concentration than green
liquor dregs, making it useful as earth construction materials
(Watkins et al., 2010). Due to its high calcium carbonate content,
primary calcareous resources can be substituted by green liquor
dregs and slaker grits, especially in building materials (Sim~ ao et al.,
2018; Siqueira and Holanda, 2013). This residue have been incor-
porated in soil-cement bricks, where it was found that the
compressive strenght increase to a optimum level with 50 wt%
(Miranda et al., 2011) or 62.5 wt% (Pinheiro et al., 2013) of addition.
Slaker grits were also applied in cement mortars (Gemelli et al.,
2001), betuminous mixtures (Modolo et al., 2010) and cement
clinker (Castro et al., 2009).
Green liquor dregs are the suspensed solids removed during
green liquor clarification, being posteriorly washed with water
containing lime sludge to pH control. This wash confers to the
residue high calcium carbonate concentration and a pH between 11
and 13, being, therefore, a high alkaline compound (Bajpai, 2015;
Nurmesniemi et al., 2005). A typical green liquor dregs composition
contains sodium carbonate (Na2CO3), calcium carbonate (CaCO3)
and sodium sulfide (Na2S), as well as some others insoluble solids
in small quantities that contains silicon, iron, aluminum, magne-
sium, manganese and sulfides (Martins et al., 2007; Nurmesniemi
et al., 2010; Po € ykio
€ et al., 2006). Martins et al. (2007) reported
these chemical elements in proportions of 0.79, 1.0, 0.38, 1.39, 0.85
and 0.97% (mass/mass), respectively.
~o et al. (2018)).
Slaker grits is generated at the bottom of the lime slaker that
converts calcium oxide (CaO) into calcium hydroxide (Ca(OH)2) on
its recovery process (Sima ~o et al., 2018). This residue has a granu-
lated appearance and gray color (Miranda et al., 2011), and is
consisted in its majority of calcium carbonate (CaCO3), but residual
amounts of CaO, Ca(OH)2 and Na2CO3 may also be present
(Machado et al., 2007). Metalic ions such as barium, chromiun,
copper, nickel and zinc may be found in very small quantities
(Monte et al., 2009). According with the reports of Po € ykio
€ et al.
(2014), the total concentration of these elements are, respectively,
230, 15, 2.6, 33 and 33 mg kg1 pH is also highly alkaline, with
values between 12.6 and 12.8 (Po € ykio
€ et al., 2006; Cabral et al.,
2008).
Once green liquor dregs and slaker grits represents larger frac-
tion of solid wastes generated at pulp and paper mills and are
recognized by high calcium carbonate contents (Sima ~o et al., 2018;
Castro et al., 2009), essential raw material of the ceramic industry
and, thus, great application potential in its traditional products
used in construction, the aim of this project is to characterize these
two residues by its chemical and mineralogical composition, ther-
mal and morphological behavior. From the systematic character-
ization of both solid residues with the mentioned techniques, for
the first time reunited in one single work aiming traditional
ceramic products, potential future application fields of green liquor
dregs and slaker grits will be identified, in order to turn feasible its
consumption as alternative raw material to the detriment of its
landfilling, and also contributing to greater sustainability of related
productive chains.
2. Materials and methods
Green liquor dregs (dregs) and slaker grits (grits) were obtained
from a Brazilian pulp and paper mill. The residues were dried at
110
C for 48 h and separately milled on hammer miller in order to
obtain fine particles smaller than 106 mm, and then subject to the
same characterization methods.
The chemicals compositions of the residues were obtained by X-
ray fluorescence spectrometer (XRF; PANalytical, Zetium) on
calcareous calibration of the samples fused with anhydrous lithium
tetraboride at 1200
C for 2 h. Crystalline structures of the residues
were obtained by X-ray diffraction (XRD; X'Pert Pro e PANalytical-
X'Celerator) using CuKa radiation at 40 kV and 30 mA. The patterns
were recorded from 10
to 90
(2q) range with a step scanning of
0.02
/s and a duration time of 10 s for each step. The diffractograms
were interpreted using data banks of JCPDS. The presence of
organic matter and major inorganic bonds was evaluated by
infrared spectroscopy (FTIR; iS5-Nicolet Thermo FT-IR) on KBr
pellets, between 4000 and 400 cm1 with a 4 cm1 resolution and
32 scans. Samples and KBr salt were previously dried in an oven at
110
C for 24 h.
 V. Ribeiro dos Santos et al. / Journal of Cleaner Production 240 (2019) 118220 3

Table 1
Chemical composition of green liquor dregs and slaker grits under study by XRF method and from described references.

Waste Oxide contents (wt%)

CaO MgO SiO2 Al2O3 Fe2O3 Na2O K2O P2O5 TiO2 SrO MnO SO3 LOIa

Dregs 33.00 4.65 2.35 0.69 0.65 11.70 1.03 0.33 <0.10 <0.10 0.37 2.82 42.10
Mymrin et al. (2017) 37.4 5.1 2.8 0.5 0.5 4.5 0.3 0.2 e e 0.3 1.6 46.8
Lage et al. (2016) 46.2 3.3 1.3 0.43 0.8 3.4 0.28 3.3 <0.03 0.14 0.41 1.4 38.5

Grits 55.80 0.47 1.31 0.42 <0.10 0.60 <0.10 0.65 <0.10 0.13 <0.10 0.11 40.10
Mymrin et al. (2017) 50.8 0.3 3.5 0.4 0.4 4.5 0.3 0.5 e e e 1.7 37.6
Siqueira and Holanda (2018) 68.67 e e e e e 1.04 e e 0.16 e 1.6 29.08
a
LOI ¼ Loss on ignition (at 1200
C).

The particles size distributions were obtained by laser diffrac-
tion (CILAS 1190) of the suspension in water using DARVAN® as
deflocculant, with a working range of 0.04 mme250.00 mm, and the
surface area were determined in a surface area analyzer (Quan-
tachrome, NOVA, 4200e) and density by helium pycnometer
(Quantachrome, Ultrapyc 1220e) of the previously dried samples.
The morphologies were analyzed by scanning electron spectros-
copy (SEM; JOEL-6400) of the samples coated with Au (Quarum,
Q150R ES).
Thermogravimetric analysis (TGA; NETZSCH, Iris TG 209 F) was
performed in order to obtain the mass loss and principal thermal
events occurrence temperature was obtained from its derivate
curve. Samples were heated to 1000
C at 20
C/min on nitrogen
atmosphere and TG and DTG curves were collected.
3. Results and discussion
3.1. Chemical and mineralogical characterization
Table 1 shows the chemical composition of green liquor dregs
and slaker grits under study by XRF and a few ones reported by
Mymrin et al. (2017), Lage et al. (2016) and Siqueira and Holanda
(2018).
Trace components not listed can also be present in concentra-
colored glasses (Conserva et al., 2014). MgO and Al2O3 are
commonly used as intermediated agents of vitreous masses, acting
as stabilizers.
Fig. 2 shows XRD patterns of green liquor dregs and slaker grits.
The diffractograms of both wastes reveals CaCO3 in calcite form as
dominant phase, agreeing with literature founds (Martins et al.,
2007; Watkins et al., 2010; Castro et al., 2009; Nurmesniemi
et al., 2010). As reported by Lage et al. (2016), small traces of
dolomite [CaMg(CO3)2] where identified on both residues, and
cesanite [Ca2Na3(SO4)3(OH)] on green liquor dregs. Indicative peaks
of quartz (SiO2) are in agreement with Mymrin et al. (2017), and
natrite (Na2CO3) with Siqueira and Holanda (2013) and Castro et al.
(2009). In the literature there are works that reports the presence of
pirssonite (CaNa2(CO3)2.2H2O) (Martins et al., 2007; Lage et al.,
2016), magnesium oxide (MgO) (Novais et al., 2018), wustite
(FeO) and calcium hydroxide [Ca(OH)2)] (Martins et al., 2007;
Torres et al., 2017), but these crystalline structures were not iden-
tified on the XRD patterns.
FTIR spectra of green liquor dregs and slaker grits are shown in
Fig. 3. By means of comparison, infrared spectra of commercial
calcium carbonate (Synth, C1004.01. AH) was added. It can be
observed all the bands expected of calcium carbonate is present on
both wastes, been assigned to on-the-plane flexural vibration (y4)
1
of the CO23 group at 715 cm , out-of-plane flexural vibration (y2)
of the CO3 group at 877 cm1, asymmetric deformation vibration
2

tions below equipment measurement capacity. Results allows to (y3) of the CO2 3 group at 1427 cm1 and vibration of C]O
verify the high CaO content on the residues, corresponding to 33.0% stretching at 1800 cm1 (Xia et al., 2015). Combination bands at
in green liquor dregs and 55.8% in slaker grits. The MgO content 2509 cm1 (2y2 þ y4) and at 2873/2983 cm1 (2y3) can also be
differ significantly, corresponding to 4.65% and 0.47%, respectively. observed on slaker grits residue (Legodi et al., 2001). The absence of
Alkaline oxides such as Na2O and K2O were also identified with a strong band between 1070 and 1080 cm1, which represents the
great quantities on green liquor dregs when compared with slaker vibration mode (y1), confirms that the calcium carbonate is in the
grits, achieving values equal to 11.7 and 1.03% on the first residue
and 0.6 and > 0.1% on the second. Other oxides relevant to ceramic
formulations like SiO2 and Al2O3 appears with low content.
Considering the major presence of inorganic compounds different
from CaO on green liquor dregs, it is safe to assume high CaCO3
purity on slaker grits.
It is verified the identified oxides of low contents presents
values very alike and do not vary in great quantities when
compared with literature data. However, CaO varies in about 10 wt
% for both residues and Na2O presents values over two times higher
than describe in the literature for green liquor dregs. According
with the results and literature data the oxides content in both
wastes vary due to its sources, raw materials and processing
methods adopted by pulp and paper mills (Castro et al., 2009).
Considering ceramic products, oxides other than CaO revealed
by XRF are of great use. Alkaline compounds like Na2O and K2O are
fluxing agents, able weaken chemical bonds and result in melting
temperature decrease of vitreous masses (Yoshihiro et al., 2016) or
reduction of sintering temperature of clay (Sokolar, 2018). Chro- Fig. 2. XRD patterns of green liquor dregs and slaker grits. Legend A e Calcite (CaCO3),
mophores ions such as Fe and Ti provides color alteration that tends B e Quartz (SiO2), , e Dolomite [CaMg(CO3)2], - e Cesanite [Ca2Na3(SO4)3(OH)]
to red and white, respectively, being of great interest on glazes or and ◊ e Natrite (Na2CO3).
4 V. Ribeiro dos Santos et al. / Journal of Cleaner Production 240 (2019) 118220
Fig. 3. FTIR spectra of green liquor dregs and slaker grits in comparison with com-
mercial calcium carbonate.
form of calcite on all samples, once the bond representing this band
is infrared inactive due to the symmetry of calcite crystals (Legodi
et al., 2001). On green liquor dregs, the band at 1109 cm1 repre-
sents the SO24 from cesanite [Ca2Na3(SO4)3(OH)], as indicated by
XRD, and the band at 1647 cm1 represents the C]C axial defor-
mation of organic material (Martins et al., 2007; Almeida et al.,
2007), probably corresponding to traces of coal, cellulose and/or
lignin from the processing steps at pulp and paper mills. These
results are in agreement with the founds of Martins et al. (2007)
and Almeida et al. (2007).
The influence of organic matter on ceramics is well illustrated
with clay, that naturally contain organic compounds, which helps
on the obtention of more plastic masses (Bormans, 2004). The
presence of lignin fibers in ceramics allows the preparation of
smooth clay slips, and is also able to reduce breakage and chipping
of unfired ceramic products (Harkin, 1969). Coal incorporated to
ceramics and glass-ceramics results in desirable properties attrac-
tive to industrial use in construction (Kim and Kim, 2004; Erol et al.,
2008). Some ceramic products use organic matter on formulations
to obtain determined properties, such as bricks fabricated from
clay, which uses glycerin, sawdust, paper sludge and coal as
Fig. 4. (a) Differential and (b) cumulative volumetric particle size distribution of green liquor dregs and slaker grits.
sacrifice material to pore formation to enhance insulation capacity
(Demir, 2008; Martínez-Martínez et al., 2016). Organic pore for-
mers are cheap and ensure heat capacity to furnace while firing,
and once paper sludge and coal are already used as pore formers,
green liquor dregs may have great reuse potential in similar
application.
3.2. Physical and morphological characterization
Differential and cumulative volumetric particle size distribution
are shown in Fig. 4, revealing a predominant monomodal behavior
and similar particle size distribution forms that differ on diametral
ranges. Green liquor dregs presented a mean particle size of
11.63 mm (D50 value) and a particle size distribution ranging from
2.79 (D10 value) and 23.15 mm (D90 value). Although this physical
property widely varies with adopted processing method, literature
reveals green liquor dregs has very fine particles, just as observed
(Modolo et al., 2010; Novais et al., 2018). Slaker grits presented a
mean particle size of 24.13 mm (D50 value) and a particle size dis-
tribution ranging from 4.34 (D10 value) to 44.70 mm (D90 value).
Wide ranges of particles sizes for this residue was also found by
Siqueira and Holanda (2013).
Physical properties of both residues are summarized on Table 2.
Green liquor dregs and slaker grits density values were
2.4981 g/cm3 and 2.7027 g/cm3, respectively, and are in close
agreement with founds in literature (Modolo et al., 2010; Lage et al.,
2016; Torres et al., 2017). The green liquor dregs surface area ob-
tained was 72.084 m2/g and expressively diverge with results ob-
tained by Torres et al. (2017) of 1.031 m2/g and by Lage et al. (2016)
of 6.24 m2/g. This result suggests organic matter contribution to
this property, as identified on the FTIR spectra. The fine particle size
distribution combined with high surface area may result in
elevated reactivity on green liquor dregs. Slaker grits surface area
was 2.901 m2/g, and this value is triple of the one obtained by
Torres et al. (2017) of 0.972 m2/g.
SEM micrographs are shown in Fig. 5, where irregular-shaped
particles typical of calcite are evidenced in both powdered resi-
dues. Larger particles size resembles an agglomerate of small
Table 2
Physical properties of green liquor dregs and slaker grits.
Property Green liquor dregs Slaker grits
Mean particle size (mm) 11.63 24.13
Density (g/cm3) 2.4981 2.7027
Surface area (m2/g) 72.084 2.901
 V. Ribeiro dos Santos et al. / Journal of Cleaner Production 240 (2019) 118220
particles, and may be the cause of the high irregularity observed.
Similar micrographs were obtained by Novais et al. (2018) for green
liquor dregs and by Siqueira and Holanda (2013) for slaker grits.
3.3. Thermal characterization
Fig. 6 shows TG/DTG curves of both residues and CaCO3 curves
were also added for comparison, where the only event (1) at 740
C
represents its decarbonation due to calcite pyrolysis. Green liquor
dregs TG curve indicates a weight loss of 43%, consistent with that
obtained by XRF (Table 1), and DTG curve reveals the occurrence of
tree thermal events; one around 400
C (2) with a weight loss of 8%,
another at 720
C (1) with a weight loss of 35%, and finally between
820 and 920
C (3), representing the decomposition of natrite,
calcite and organic matter, respectively.
The organic matter is most likely to be carbonized lignin and the
last thermal event represents its final decomposition, which is
accompanied by constant mass loss over the entire temperature
range. According with Oliveira et al. (2017), the carbonized lignin
great thermal stability is a consequence of its condensation and
hydroxyls presence on its organic structure, with occurrence of
intermediated products formation that add the steps number till its
final decomposition. Also, by comparing the carbonized lignin
morphology presented on the work of Oliveira et al. (2017) and
green liquor dregs on Fig. 5, similarities can be found. Summing this
residue high specific surface area with the morphology and thermal
Fig. 5. SEM micrographs of (a, b) green liquor dregs and (c, d) slaker grits.
5
results, the organic matter is most likely to be carbonized lignin.
Almeida et al. (2007) also analyzed green liquor dregs by its ther-
mal behavior and found one event only, attributed to calcium car-
bonate pyrolysis at 753
C with a weight loss of 38.4%, and Martins
et al. (2007) found that calcium carbonate decarbonation on green
liquor dregs occur at 890
C with a weight loss of 33.5%.
Slaker grits TG curves indicates a weight loss of 40% and DTG
curve one single event at 760
C, corresponding to calcium car-
bonate decomposition. Destefani et al. (2010) reported the occur-
rence of this event at 941
C and a 42% weight loss, and Martins
et al. (2007) at 840
C with a weight loss of 14.5% attributed to
this specific decomposition.
The difference between the CaCO3 decomposition temperature
of analyzed wastes may be due to the smallest particle size of green
liquor dregs and its high reactivity, as suggested in section 2.3.
Another reason is attributed to this residue alkali content (Table 1),
such as Na2CO3 and K2CO3, that even at 1 wt% are able to reduce
calcium carbonate decomposition temperature (Chattaraj et al.,
1973). Slaker grits decomposition temperature gets closer of a
standard calcium carbonate, probably due to its higher purity once
it is removed from the Kraft process after green liquor dregs. The
weight loss difference may be attributed to processes methods
variation at pulp and paper mills that results in diverse CaCO3
content, and its obtained decompositions temperatures, that differ
from those in literature, vary in values for the same reason (Martins
et al., 2007).
6 V. Ribeiro dos Santos et al. / Journal of Cleaner Production 240 (2019) 118220
Fig. 6. TG and DTG curves of green liquor dregs and slaker grits in comparison with
commercial calcium carbonate.
The determination of the CaCO3 decomposition temperature
becomes an important analysis considering the ceramic processing.
In some cases, calcite needs to be completely decomposed to allow
further steps. In the single-fired manufacturing process of wall tiles,
for example, total decomposition should be achieved before the
glaze melts and seals the tile surface in order to prevent bubbles as
a result of the CO2 release during calcite pyrolysis (Escardino et al.,
2013). Considering a future application of the residues on ceramic
products, slaker grits may be preferable in order to avoid processing
changes on consolidated ceramic industries.
3.4. Critical analysis
Although green liquor dregs and slaker grits shown to have
properties much alike calcium carbonate, proving to be an excellent
source of this raw material, challenges may prevent residues uses
on large scales on ceramic products industries. Since they are solid
wet wastes in block form, drying and milling pre-treatment steps
are needed in order to allow its handling, storage and use.
Furthermore, properties and characteristics may differ according to
the lot and pulp and paper mills, as observed by comparing the
obtained results with the literature, making it necessary to redo the
characterization analysis to each lot received.
Comparing both residues results and its origin on Kraft process,
it can be stated that due to the earlier removal of green liquor dregs,
the residue in question presents great quantities of calcium car-
bonate organic and inorganic contaminants but, as discussed, these
may provide specific characteristics attractive for ceramic products.
Slaker grits, on the other hand, has high CaCO3 purity and great
total substitution potential on formulations.
From this study, it is clear green liquor dregs and slaker grits
residues from pulp and paper mills are being literally wasted with
its landfilling. Able to incorporate clay, concrete, glasses and great
majority of other ceramic products, these residues use will generate
excellent benefit-cost ratio to industries and environment. Pulp and
paper mills would no more spend with the landifilling high cost,
meaning economical gain, and these residues are also able to pre-
vent earth extraction of calcium carbonate and cheap source of raw
materials to ceramic industries, reflecting on a sustainable process
with no further environmental damage, closing a sustainability
cycle.
4. Conclusion
Green liquor dregs and slaker grits were analyzed by different
characterization techniques in order to evaluate its potential to
incorporate or substitute ceramic industries raw materials on its
traditional products. For the first time, all the properties analyzed
are reunited in one single work focusing this eco-friendly applica-
tion. XRF and XRD analysis proved the high calcium carbonate
content in calcite form on both residues, especially on slaker grits,
and also carbonates of sodium and magnesium on green liquor
dregs. FT-IR spectra revealed the presence of organic matter on
green liquor dregs that are probably wood organic constituents
such as cellulose and lignin, or even coal. Physical and morpho-
logical characterization revealed smaller irregular-shaped particle
size and bigger surface area for green liquor dregs compared to
slaker grits. TGA analysis shown the thermal decomposition events
calcium carbonates at 720
C and 760
C to green liquor dregs and
slaker grits, respectively. From these results, it is clear the high
incorporation potential of this wastes on ceramic formulations.
Slaker grits, however, is purer than green liquor dregs once it has
higher CaCO3 content and less inorganic and organic impurities,
besides closer decomposition temperature to this standard raw
material on industries, being, therefore, great incorporation and
substitution feasibility on ceramic traditional products.
Declarations of interest
None.
Acknowledgements
The authors would like to thank CAPES for the financial support
to this work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2019.118220.
References
Almeida, H.C., Silveira, C.B., Ernani, P.R., Campos, M.L., Almeida, D., 2007.
Composiça ~o química de um resíduo alcalino da indústria de papel e celulose
(DREGS). Quim. Nova 30, 1669e1672. https://doi.org/10.1590/S0100-
40422007000700032.
Andreola, R., Jorge, R.M., Santos, O.A., Jorge, L.M., 2011. Modeling, simulation, and
analysis of a reactor system for the generation of white liquor of a pulp and
paper industry. Braz. Arch. Biol. Technol. 54, 197e206. https://doi.org/10.1590/
S1516-89132011000100024.
Bajpai, P., 2015. Green Chemistry and Sustainability in Pulp and Paper Industry, first
ed. Springer International Publishing. Green Chemistry and Sustainability in
Pulp and Paper Industry. https://doi.org/10.1007/978-3-319-18744-0.
Bormans, P., 2004. Ceramics Are More than Clay Alone. Cambridge International
Science Publishing, Cambridge.
Cabral, F., Ribeiro, H., Hil
ario, L., Machado, L., Vasconcelos, E., 2008. Use of pulp mill
inorganic wastes as alternative liming materials. Bioresour. Technol. 99,
8294e8298. https://doi.org/10.1016/j.biortech.2008.03.001.
Castro, F., Vilarinho, C., Trancoso, D., Ferreira, P., Nunes, F., Miragaia, A., 2009. Uti-
lisation of pulp and paper industry wastes as raw materials in cement clinker
production. Int. J. Mater. Eng. Innov. 1, 74. https://doi.org/10.1504/ijmatei.2009.
024028.
Chattaraj, B.D., Dutta, S.N., Iyengar, M.S., 1973. Studies on the thermal decomposi-
tion of calcium carbonate in the presence of alkali salts (Na2Co3, K2CO3and
NaCl). J. Therm. Anal. 5, 43e49. https://doi.org/10.1007/BF01914472.

Conserva, L.R., Nastri, S., Leite, A.P., Melchiades, F.G., Boschi, A.O., 2014. Ions
Cromo foros e a Cor de Queima de Porcelanatos Esmaltados. Ceram. Ind 19,
13e16. https://doi.org/10.4322/cerind.2014.073.
Demir, I., 2008. Effect of organic residues addition on the technological properties of
 V. Ribeiro dos Santos et al. / Journal of Cleaner Production 240 (2019) 118220
clay bricks. Waste Manag. 28, 622e627. https://doi.org/10.1016/j.wasman.2007.
03.019.
Destefani, A., Santos, M.M., Holanda, J.N., 2010. Caracterizaça ~o e avaliaça
~o do resí-
duo “grits” da indústria de celulose. In: 19o Congresso Brasileiro de Engenharia
e Cie^ncia Dos Materiais. Campos do Jorda ~o, Brazil.
Erol, M., Küçükbayrak, S., Ersoy-Meriçboyu, A., 2008. Comparison of the properties
of glass, glass-ceramic and ceramic materials produced from coal fly ash.
J. Hazard Mater. 153, 418e425. https://doi.org/10.1016/j.jhazmat.2007.08.071.
Escardino, A., García-Ten, J., Saburit, A., Feliu, C., Go mez-Tena, M.P., 2013. Calcium
carbonate decomposition in white-body tiles during firing in the presence of
carbon dioxide. Ceram. Int. 39, 6379e6390. https://doi.org/10.1016/j.ceramint.
2013.01.064.
GEDF-CD/FIEP, 2016. Panorama Setorial Indústria de celulose, papel, embalagens e
artefatos de papel. WWW Document. http://www.fiepr.org.br/para-sindicatos/
estudos-economicos/uploadAddress/papel_digital[75083].pdf, 3.26.19.
Gemelli, E., Camargo, N., Brescansin, J., 2001. Evaluation of paper industry wastes in
construction materials applications. Mater. Res. 4, 297e304. https://doi.org/10.
1590/S1516-14392001000400013.
Golmaei, M., Kinnarinen, T., Jernstro €m, E., H€ akkinen, A., 2018. Extraction of haz-
ardous metals from green liquor dregs by ethylenediaminetetraacetic acid.
J. Clean. Prod. 212, 219e227. https://doi.org/10.1016/j.jenvman.2018.01.078.
Harkin, J.M., 1969. Lignin and its Uses 1e9.
Kim, J.M., Kim, H.S., 2004. Processing and properties of a glass-ceramic from coal fly
ash from a thermal power plant through an economic process. J. Eur. Ceram.
Soc. 24, 2825e2833. https://doi.org/10.1016/j.jeurceramsoc.2003.08.012.
Kinnarinen, T., Golmaei, M., Jernstro€ m, E., Ha €kkinen, A., 2016. Separation, treatment
and utilization of inorganic residues of chemical pulp mills. J. Clean. Prod. 133,
953e964. https://doi.org/10.1016/j.jclepro.2016.06.024.
Lage, I.M., Lizancosa, M.V., Burgo, P.V., Ferna ndez, M.R., Herrero, C.V.,
Rodríguez, A.R., Cano, M.M., 2016. Concretes and mortars with waste paper
industry: biomass ash and dregs. J. Environ. Manag. 181, 863e873. https://doi.
org/10.1016/j.jenvman.2016.06.052.
Legodi, M.A., De Waal, D., Potgieter, J.H., 2001. Quantitative determination of CaCO3
in cement blends by FT-IR. Appl. Spectrosc. 55, 361e365. https://doi.org/10.
1366/0003702011951786.
Machado, C.C., Pereira, R.S., Lima, D.C., Carvalho, C.A., Pires, D.M., 2007.
Caracterizaça ~o tecnologica de misturas solo-grits para pavimentaç~ ao de estra-
das florestais: influe ^ncia do tratamento te rmico do grits na resiste
^ncia mec^anica
das misturas. Rev. 
Arvore 31. https://doi.org/10.1590/S0100-
67622007000300014.
Mahmoudkhani, M., Richards, T., Theliander, H., 2004. Recycling of solid residues to
the forest: experimental and theoretical study of the release of sodium from
lime mud and green liquor dregs aggregates. Process Saf. Environ. 82, 230e237.
https://doi.org/10.1205/095758204323065993.
Ma€kel€a, M., Geladi, P., Grimm, A., Dahl, O., Pietil€ ainen, A., Larsson, S.H., 2016.
Cyclone processing of green liquor dregs (GLD) with results measured and
interpreted by ICP-OES and NIR spectroscopy. Chem. Eng. J. 304, 448e453.
https://doi.org/10.1016/j.cej.2016.06.107.
Ma€kel€a, M., Harju-Oksanen, M., Watkins, G., Ekroos, A., Dahl, O., 2012. Feasibility
assessment of inter-industry solid residue utilization for soil amendmentd-
trace element availability and legislative issues. Resour. Conserv. Recycl. 67, 1e8.
https://doi.org/10.1016/j.resconrec.2012.06.012.
Manskinen, K., Nurmesniemi, H., Po €ykio€ , R., 2011. Total and extractable non-process
elements in green liquor dregs from the chemical recovery circuit of a semi-
chemical pulp mill. Chem. Eng. J. 166, 954e961. https://doi.org/10.1016/j.cej.
2010.11.082.
Martínez-Lage, I., Velay-Lizancos, M., Va zquez-Burgo, P., Rivas-Fern andez, M.,
Vazquez-Herrero, C., Ramírez-Rodríguez, A., Martín-Cano, M., 2016. Concretes
and mortars with waste paper industry: biomass ash and dregs. J. Environ.
Manag. 181, 863e873. https://doi.org/10.1016/j.jenvman.2016.06.052.
Martínez-Martínez, S., Pe rez-Villarejo, L., Eliche-Quesada, D., Carrasco-Hurtado, B.,
Sanchez-Soto, P.J., Angelopoulos, G.N., 2016. Ceramics from clays and by-
product from biodiesel production: processing, properties and microstruc-
tural characterization. Appl. Clay Sci. 121e122, 119e126. https://doi.org/10.1016/
j.clay.2015.12.003.
Martins, F.M., Martins, J.M., Ferracin, L.C., Cunha, C.J., 2007. Mineral phases of green
liquor dregs, slaker grits, lime mud and wood ash of a Kraft pulp and paper mill.
J. Hazard Mater. 147, 610e617. https://doi.org/10.1016/j.jhazmat.2007.01.057.
Melo, J.R., Medeiros, J.F., Marques, R.G., Andrade, A.A., 2011. Estudo das caracter-
ísticas do licor negro. Rev. Eng. e Tecnol. 3, 1e11.
Miranda, L.D., Alvarnga, R.D., Junior, P.C., Júnior, E.D., Carvalho, C.A., Fassoni, D.P.,
7
Couto, L.G., 2011. Avaliaç~ ao do potential do grits como material de construç~ ao
na produç~ ao de tijolos de solo-cimento. Rev. Arvore  35.
Modolo, R., Benta, A., Ferreira, V.M., Machado, L.M., 2010. Pulp and paper plant
wastes valorisation in bituminous mixes. Waste Manag. 30, 685e696. https://
doi.org/10.1016/j.wasman.2009.11.005.
Monte, M., Fuente, E., Blanco, A., Negro, C., 2009. Waste management from pulp and
paper production in the European Union. Waste Manag. 29, 293e308. https://
doi.org/10.1016/j.wasman.2008.02.002.
Mymrin, V., Cusma, D.F., Rissardi, J.L., Cavalin, F.L., Correia, R.A., Rolim, P.H.,
Pedroso, C.L., 2017. Utilizaç~ ao de resíduos de produça ~o de papel e celulose para
fabricaç~ ao de materiais de construça ~o ambientalmente limpos. In: 8
Fo rum
Internacional de Resíduos So lidos. Curitiba, Brazil.
Novais, R.M., Cavalheiras, J., Senf, L., Labrincha, J.A., 2018. Upcycling unexplored
dregs and biomass fly ash from the paper and pulp industry in the production
of eco-friendly geopolymer mortars: a preliminary assessment. Constr. Build.
Mater. 184, 464e472. https://doi.org/10.1016/j.conbuildmat.2018.07.017.
Nurmesniemi, H., Po €ykio€, R., Pera€ma €ki, P., Kuokkanen, T., 2005. The use of a
sequential leaching procedure for heavy metal fractionation in green liquor
dregs from a causticizing process at a pulp mill. Chemosphere 61, 1475e1484.
https://doi.org/10.1016/j.chemosphere.2005.04.114.
Nurmesniemi, H., Watkins, O.D., Po € ykio
€, R., 2010. Slaker grits from the causticising
process of a pulp mill e a potential fertiliser and liming agent material for use
in agriculture and forestry. IJMatEI 1, 312e324. https://doi.org/10.1504/ijmatei.
2010.035159.
Oliveira, C.P., Pimenta, G.H., Silva, M.R., Ramos, M.M., Siqueira, M., Fonseca, Y.A.,
2017. Extraç~ ao da lignina presente no licor negro para adsorç~ ao de íons de
metais pesados. Perc Acad 7 (14), 468e482.
€
Osterås, A.H., Sunnerdahl, I., Greger, M., 2005. The impact of wood ash and green
liquor dregs application on Ca, Cu, Zn and Cd contents in bark and wood of
Norway spruce. Water Air Soil Pollut. 166, 17e29. https://doi.org/10.1007/
s11270-005-7747-0.
Pinheiro, M., Alvarenga, R., Ribeiro, B., Júnior, P., Sarmet, M., Fassoni, D., 2013.
Avaliaç~ ao experimental de blocos prensados de solo-cimento com adiç~ ao de
grits. Ambient. Construído 13, 29e46.
€ykio
Po €, R., Nurmesniemi, H., Dahl, O., Watkins, G., Manskinen, K., 2014. Evaluation
of the bio-accessible non-process element concentrations in slaker grits by
synthetic sweat and gastric fluids extraction. J. Environ. Occup. Sci. 3, 65.
https://doi.org/10.5455/jeos.20140315081719.
€ykio
Po €, R., Nurmesniemi, H., Kuokkanen, T., Pera €ma €ki, P., 2006. Green liquor dregs
as an alternative neutralizing agent at a pulp mill. Environ. Chem. Lett. 4,
37e40. https://doi.org/10.1007/s10311-005-0031-0.
Saikia, N., Kato, S., Kojima, T., 2007. Production of cement clinkers from municipal
solid waste incineration (MSWI) fly ash. Waste Manag. 27, 1178e1189. https://
doi.org/10.1016/j.wasman.2006.06.004.
Sim~ao, L., Hotza, D., Raupp-Pereira, F., Labrincha, J.A., Montedo, O.R.K., 2018. Wastes
from pulp and paper mills - a review of generation and recycling alternatives.
Cera^mica 64, 443e453. https://doi.org/10.1590/0366-69132018643712414.
Siqueira, F., Holanda, J., 2013. Reuse of grits waste for the producion of soil-cement
bricks. J. Environ. Manag. 131, 1e6. https://doi.org/10.1016/j.jenvman.2013.09.
040.
Siqueira, F.B., Holanda, J.N., 2018. Application of grits waste as a renewable car-
bonate material in manufacturing wall tiles. Ceram. Int. 44, 19576e19582.
https://doi.org/10.1016/j.ceramint.2018.07.203.
Sokolar, R., 2018. Sintering of whiteware body depending on different fluxing
agents and binders. In: Shishkovsky, I. (Ed.), Sintering of Functional Materials.
IntechOpen, pp. 45e76. https://doi.org/10.5772/intechopen.68501.
Torres, C.M., Silva, C.M., Pedroti, L.G., Fernandes, W.E., Ballotin, F.C., Zanuncio, J.C.,
2017. Cement Portland production with dregs and grits from kraft pulp mills
incorporated to clinker. In: 6th International Workshop j Advances in Cleaner
Production. S~ ao Paulo, Brazil.
Watkins, G., Po €ykio € , R., Nurmesniemi, H., Dahl, O., 2010. Earth construction and
landfill disposal options for slaker grits. Res. J. Appl. Sci. Eng. Technol. 2,
757e764.
Xia, M. -s., Yao, Z. -t., Ge, L. -q., Chen, T., Li, H. -y., 2015. A potential bio-filler: the
substitution effect of furfural modified clam shell for carbonate calcium in
polypropylene. J. Compos. Mater. 49, 807e816. https://doi.org/10.1177/
0021998314525981.
Yoshihiro, S., Yonemura, T., Masuno, A., Inoue, H., Ohara, K., Kohara, S., 2016.
Structural change of Na2O-doped SiO2 glasses by melting. J. Ceram. Soc. Jpn.
124, 717e720. https://doi.org/10.2109/jcersj2.16028.