Construction and Building Materials 184 (2018) 464–472

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Construction and Building Materials

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

Upcycling unexplored dregs and biomass fly ash from the paper and
pulp industry in the production of eco-friendly geopolymer mortars:
A preliminary assessment
Rui M. Novais a,⇑, J. Carvalheiras a, L. Senff b, J.A. Labrincha a
a
Department of Materials and Ceramic Engineering/CICECO – Aveiro Institute of Materials, University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal
b
Mobility Engineering Center, Federal University of Santa Catarina (UFSC), 89218-000 Joinville, SC, Brazil

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Two unexplored waste streams from

pulp and paper industry were
investigated.
 Dregs were used for the first time as
filler in geopolymeric mortars
production.
 Biomass fly ash was used as main
aluminosilicate source (75 wt%).
 Dregs enhanced mortars’ tensile (up
to 71%) and compressive strength (up
to 34%).
 Using dregs as additives in
geopolymers is an effective waste
recycling strategy.

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

Article history: Green liquor dregs wastes coming from pulp and paper production are currently disposed in landfills at a
Received 29 January 2018 huge cost for industry and the environment. In this work, a novel and more sustainable waste manage-
Received in revised form 2 July 2018 ment strategy is proposed. Dregs were used for the first time as fine filler in the production of biomass fly
Accepted 5 July 2018
ash-based geopolymeric mortars. The influence of the dregs incorporation amount on the fresh (geopoly-
Available online 9 July 2018
mer kinetics and mortars workability) and hardened-state (mechanical resistance, water absorption and
capillary water absorption) properties of the mortars was evaluated. Although dregs incorporation reduce
Keywords:
the flow workability (up to 19%), their presence and amount did not significantly alter the geopolymer-
Green liquor dregs
Biomass fly ash
ization kinetics. Additionally dregs-containing mortars exhibited enhanced tensile (up to 71%) and com-
Inorganic polymer pressive strength (up to 34%), and lower water absorption in comparison with the reference mortar.
Calorimetry These results demonstrate the feasibility of using dregs as fine filler in geopolymers production.
Mechanical resistance Moreover the mortars were produced using mainly biomass fly ash waste as aluminosilicate source
which further reduces the environmental impact of the pulp and paper industry.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction European countries, accounting for 7% of all EU pulp production

[1]. However this industry is also responsible for a distressing
The pulp and paper production is one of the most vital indus- amount of residues (11 million tons generated in Europe) [2], the
trial activities in Portugal, which is ranked in third place amongst most abundant being dregs, grits and biomass ash. Among these,
dregs are the most challenging residue since there is currently no
⇑ Corresponding author. viable solution for their recycling. Dregs worldwide production is
E-mail address: [email protected] (R.M. Novais). unknown. However an estimated production of 0.5 and 1.3 million

https://doi.org/10.1016/j.conbuildmat.2018.07.017
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
 R.M. Novais et al. / Construction and Building Materials 184 (2018) 464–472 465

tons was reported by Kinnarinen et al. [3], considering a global pro- 2. Experimental conditions
duction of 117 million tons of Kraft pulp. Recent data shows an
2.1. Materials
even higher amount (178.8 million tons) [1], which raises the dregs
annual production to values ranging from 0.7 to 2.0 million tons. In this investigation biomass FA and dregs wastes, produced by a Portuguese
Dregs are usually dumped in landfills [4], which is environmentally paper pulp plant, were used as main aluminosilicate source (75 wt%) and as fine fil-
unsustainable. In addition over the past years landfill tax has been ler, respectively. The FA was used without any pre-treatment step, albeit their
coarse particle size distribution that will negatively affect the geopolymerization
increasing [5], while existing landfills are progressively reaching
extension. Nevertheless milling or sieving was avoided to reduce the geopolymer
exhaustion. These environmental and economic concerns exert production cost. As for the dregs they were supplied as very large solid blocks
pressure on the paper and pulp industry to change the paradigm containing 46 wt% water. The dregs were dried, crushed in a mortar and then
from conventional linear concept to the circular economy. Indeed sieved through a 75 mm mesh prior to mixing.
the increasing public awareness regarding environmental issues Benchmark metakaolin (MK) (ArgicalTM M1200S; Univar) was also used in the
compositions (25 wt%) to ensure suitable molar ratios. To promote alkaline activa-
is an important driver for the development of new and more sus-
tion a mixture of sodium silicate (H2O = 62.1 wt%; SiO2/Na2O = 3.15; Quimialmel)
tainable waste management strategies. and 10 M sodium hydroxide solution (ACS reagent, 97%; Sigma Aldrich) was used.
Dregs are produced during the clarification of the green liquor The sand employed as an aggregate was composed by particles ranging from
and consist of insoluble residue of the smelt (which is a flux of 0.125 to 2 mm.
inorganics coming from the recuperation boiler) dissolver. Typi-
cally dregs contain sodium and calcium carbonates, sulphides, 2.2. Geopolymer mortars preparation
and an organic fraction due to incomplete burning in the recuper-
ation biomass boiler [6]. This waste is strongly alkaline (pH typi- To evaluate the influence of dregs incorporation content on the geopolymer
cally ranging from 10 to 12.8 [4]), contains high alkaline and mortars’ physical properties five formulations containing distinct dregs content
(0, 10, 15, 20 and 25 wt%) were produced (Table 1). In this study dregs were used
earth-alkaline oxides content and chlorine, which hinders their as additives, amount depending on the composition but considering the total alu-
recycling in common application, such as their incorporation in minosilicate mass (MK and FA mixture).
cement or concrete. The latter is possibly the reason for the sur- The preparation of the blends involved: i) mixing MK and FA in a plastic bag for
prisingly low number of studies in this field. Nevertheless recent 1 min; ii) homogenisation of the alkaline solution during 5 min; iii) mixture of the
aluminosilicate sources with the alkaline solution for 10 min; and iv) addition of
studies evaluated the feasibility of using dregs as aggregate in road
sand and dregs to the blend and mixture. Afterwards, the slurry was casted in
pavement construction [7] and as cement replacement in concretes metallic moulds and covered with a plastic film. The mortars were cured at 40 °C
and mortars [8]. Pasandín et al. [7] observed poor water resistance and 65% relative humidity for 24 h. afterwards the samples were demoulded and
for the dregs-containing hot-mix asphalt, which was attributed to left at ambient conditions until the 28th curing day.
the high water content of the dregs and their fineness, but also due
to their chemical composition and the increase in the mastic vis- 2.3. Materials characterisation
cosity. Martínez-Lage et al. [8] reported similar compressive and
flexural strength of the mortars in which 10% cement was replaced X-ray powder diffraction (XRD) was used to evaluate the mineralogical compo-
by dregs, while a decrease was observed for higher replacement sitions of the precursors and of the produced geopolymers using a Rigaku Geigerflex
D/max-Series instrument (Cu Ka radiation, 10–80° 2h, 0.02° 2h step-scan and 10 s
values. Still a severe fall in compressive strength for the dregs-
per step), and phase identification by PANalytical X’Pert HighScore Plus software.
containing concretes was observed, and for that reason the authors X-ray fluorescence (Philips X’Pert PRO MPD spectrometer) was used to study
have concluded that the use of dregs as replacement of cement in the chemical composition of MK, FA and dregs. The loss on ignition (LOI) at 1000
concretes is unsuitable. In this context novel management strate- °C was also determined.
Particle size distribution was determined by laser diffraction (Coulter LS230
gies that ensure valorisation of substantial amounts of dregs are
analyzer). The determination was performed by a laser diffraction technique
a pressing matter. (Fraunhofer method) for particles with a particle size from 0.4 lm to 2000 lm,
Geopolymers have attracted a lot of attention over the past and simultaneously by PIDS (Polarization Intensity Differential Scattering) to lower
years since they are considered an environmentally friendlier particle sizes (between 0.4 lm and 0.04 lm).
alternative to Portland cement [9]. This technology allows the The microstructure of the precursors and of cured geopolymeric mortars was
evaluated using scanning electron microscopy (SEM – Hitachi S4100 equipped with
use of distinct waste streams as raw materials [10–12], which fur-
energy dispersion spectroscopy, EDS – Rontec).
ther decrease their carbon footprint. Additionally, hazardous mate- In the fresh state, the influence of fine dregs on mortars was evaluated by flow
rials can be immobilized in the geopolymer network [13,14]. table test after mechanical mixing EN 1015-3 [15], while the temperature evolution
Geopolymer synthesis involves mixing aluminosilicate precursors of geopolymeric pastes upon curing was monitored in the first 10 h in a quasi-
adiabatic calorimeter under controlled relative humidity (65%) and temperature
(e.g. fly ash, metakaolin) with alkaline activators. Considering that
(40 °C). The acquisition period was selected considering a previous work by the
dregs contain very low SiO2 and Al2O3 content they cannot be used authors [16].
as a precursor in geopolymer preparation. Nevertheless they could In the hardened state, the tensile strength of mortars was evaluated after 24 h
be used as filler in geopolymeric mortars. Yet surprisingly this curing and then the compressive strength of specimens cured for 7 and 28 days was
strategy has never been exploited, up to now. determined EN 1015-11:1999 [17], using a Universal Testing Machine (Shimadzu,
model AG-25 TA) running at a displacement rate of 0.5 mm/min and the water
The present work evaluates the feasibility of using dregs as filler
absorption of the geopolymer mortars was determined by using the Archimedes
in the production of biomass fly ash (FA)-based geopolymer mor- Principle. Three specimens of each formulation were tested and the average data
tars. This is the first ever report considering the incorporation of reported.
dregs in geopolymeric mortars. In this investigation, the influence
of dregs incorporation content on the fresh (geopolymer kinetics
Table 1
and mortars workability) and hardened-state properties (compres-
Geopolymer preparation: mixture composition and NaOH molarity.
sive strength and water absorption) of the mortars was evaluated.
This investigation aims to provide a sustainable management Sample Mixture proportion (g) Spread on
name table (SD)
methodology for this unexplored waste stream, while simultane- MK FA Dregs Sodium NaOH Sand
ously decrease the knowledge gap regarding the influence of dregs silicate
incorporation in geopolymeric mortars properties. Moreover the M0 100 300 0 200 200 1200 203 ± 4
geopolymers were prepared using 75 wt% biomass FA as alumi- M10 40 188 ± 4
nosilicate source, whose recycling is still insipient, which further M15 60 174 ± 6
M20 80 170 ± 7
mitigates the pulp and paper industry wastes environmental M25 100 165 ± 7
impact.
466 R.M. Novais et al. / Construction and Building Materials 184 (2018) 464–472

Mortars’ morphology was investigated by using an optical microscope (Leica Table 2

EZ4HD). Chemical composition of metakaolin (MK), fly ash (FA) and dregs, evaluated by XRF.
The capillary water absorption of mortars specimens was determined based on
standard EN 1015-18 [18] but using specimens with 2  2  4 mm3. Components (wt%) MK FA Dregs
SiO2 54.4 34.0 2.16
TiO2 1.55 0.65 0.03
3. Results and discussion Al2O3 39.4 13.5 2.65
Fe2O3 1.75 4.95 0.68
3.1. Characterisation of the precursors MgO 0.14 3.07 8.13
CaO 0.10 16.5 15.2
MnO 0.01 0.45 0.82
The XRD patterns of dregs, FA and MK are presented in Fig. 1, Na2O – 1.52 23.8
while their chemical composition given in Table 2. As expected, K2O 1.03 5.49 0.89
the XRD pattern of the benchmark MK shows that this precursor SO3 – 2.77 10.5
is essentially amorphous, still some crystalline phases were also P2O5 0.06 1.11 0.02
Cl – 1.50 0.39
detected, namely quartz, anatase and muscovite. Its chemical com-
LOI 2.66 14.3 34.3
position reveals SiO2 and Al2O3 as dominant components. The FA is Ratio of SiO2/Al2O3 1.38 2.52 0.82
much more crystalline than MK, being quartz, calcite, and illite the
detected phases. The contents in alkaline and earth-alkaline oxides
(27%) are relatively high, which together with Cl concentration their green liquor dregs, while calcite was the dominant phase
limit the direct use of this by-product in common cement/concrete detected by Martins et al. [21]. Clearly the processing conditions
formulations. Nevertheless, and despite the lower amorphous con- in which this residue is generated affect their chemical composi-
tent of biomass FA in comparison with MK, the potential of these tion. Indeed the high sulfur content observed in our waste suggests
wastes as binder for geopolymers, if correctly combined with a poor reduction of this element in the recovery boiler. Despite the
MK, has been previously demonstrated [19,20]. relatively high LOI value shown by the dregs (suggesting the pres-
The XRD pattern of dregs show that the most abundant crys- ence of a significant organic content) the possibility of performing
talline phase is pirssonite (Na2Ca(CO3)2
2(H2O), a carbonate. Addi- pre-treatments (e.g. chemical or thermal treatments) on the waste,
tionally small amounts of calcite and magnesium oxide were also to remove the organic fraction or some of its soluble components,
detected. Accordingly Na2O and CaO are the major components that might improve the filler performance or the mortars durabil-
detected by XRF, and LOI value is expressive. The content on SO3 ity, was excluded to reduce the production cost. This topic will be
is also relevant, since this by-product result from the filtration of considered in future work.
the green-liquor that is mostly composed by Na2CO3 and Na2S. Fig. 2 presents the particle size distribution of the FA, MK and
Manskinen et al. [4] reported the existence of only pirssonite in dregs. FA show a coarser particle size distribution with a mean par-
ticle size of 59 mm, while MK has a narrower size distribution with
a mean particle size of 5 mm. Dregs are very fine with a mean par-
ticle size of 6 mm, quite similar to that observed for MK. The latter
suggests that they could be used as fine filler in geopolymers
production.
The irregular particle morphology and composition of both
wastes (FA and dregs) is illustrated by the SEM micrographs and
EDS spectra shown in Fig. 3. The elements detected by EDS are in
agreement with those determined by XRF.

3.2. Mortars characterization

3.2.1. Spread on flow table

Flow table images after fifteen strokes are shown in Fig. 4. As
observed, the addition of dregs changed the spread on table values

Fig. 1. XRD patterns of dregs, fly ash (FA) and metakaolin (MK). Fig. 2. Particle size distribution of metakaolin, fly ash and dregs.
 R.M. Novais et al. / Construction and Building Materials 184 (2018) 464–472 467

Fig. 3. SEM micrographs and EDS spectrum at two different plots of (a) dregs and (b) fly ash.

Fig. 4. Flow table images after test of geopolymeric mortars containing distinct concentration of dregs added.

of the mortars (see Table 1). ANOVA indicated a statistically signif- ratio. Moreover the fine particles of this waste (see Fig. 2) tend to
icant effect, since the p-value is lower than 0.05 (Table 3). In fact, absorb liquid solution and water molecules. This limits the maxi-
dregs-free mortar was the most fluid sample, while the 25 wt% mum dosage admissible to 25 wt%. In this work the aluminosilicate
dregs-containing mortar showed 19% reduction in the flow index (FA and MK) and the alkaline activators content was intentionally
(spreading), obviously caused by the increment of the solid/liquid kept constant in order to fully understand the influence of the
dregs incorporation on the mortar properties. Indeed geopolymer-
ization is a complex process in which the water content [22], the
Table 3 concentration of the activators [23] and the nature of the precur-
Analysis of variance (ANOVA) at a 95% confidence level for spread on table, sors [24] are known to significantly affect the geopolymerization
compressive strength and water absorption of geopolymer mortars. extension. The authors have previously shown that the slurries vis-
Mean Square F P-value cosity can be controlled by the water content and the activators
Spread on table 4.617 14.70 0.005679
concentration [16]. In this context the workability of the composi-
Compressive strength 7 days 9.650 35.87 0.000094 tions may be optimized/tailored to allow the incorporation of
28 days 14.024 7.003 0.005904 higher dregs incorporation content. This will be considered in
Water absorption 28 days 0.6381 9.661 0.002573 future work.
468 R.M. Novais et al. / Construction and Building Materials 184 (2018) 464–472

3.2.2. Calorimetric measurements

To evaluate the influence of the dregs incorporation in the
geopolymerization kinetics calorimetric measurements were per-
formed and results for the temperature evolution of the produced
mortars in the first hours upon mixing are presented in Fig. 5. All
formulations show a single peak in the first three hours due to
polymerization reactions [25]. Interestingly the presence and
amount of dregs seem not to significantly alter the reaction speed
and intensity. In fact, only a minor increase (1 °C) was observed for
the higher containing dregs mortar in comparison with the refer-
ence one. These results suggest that the dregs, in the amounts
and conditions used in this study, are not reactive or their reactiv-
ity is low. Still they contain significant amount of alkalis in their
composition which may explain the slight increase in the maxi-
mum temperature. The fresh-state properties of dregs-containing
geopolymer pastes deserves further attention, since here the high
amount of sand used in the mortars preparation may conceal the
dregs contribution to geopolymerization. It is clear that dregs
incorporation is not detrimental to geopolymerization suggesting
that it can be used as filler, at least for the incorporation levels here
reported.

3.2.3. Microstructural characterisation

XRD patterns of the reference mortar (without dregs) and of the
25 wt% dregs-containing specimens are shown in Fig. 6. As
expected, both patterns are dominated by quartz coming from
the coarse filler (sand). Still the dregs-containing mortar clearly
shows the presence of pirssonite, already detected in the waste,
suggesting that the crystalline phase is not involved in geopoly-
merization. Moreover the spectra show a right shift on the broad
hump towards higher 2h values in comparison with the spectrum
of MK, which is attributed to geopolymerization occurrence.
Interestingly despite the high amount of Na2O present in dregs Fig. 6. XRD patterns of geopolymer mortars produced without and with 25 wt%
composition none of the mortars exhibited efflorescence forma- dregs.
tion. The latter is demonstrated by the images of the specimens
shown in Fig. 7 and by the SEM micrographs present in Fig. 8. the dregs content rises the geopolymers’ tensile strength tends to
The EDS shows the expected increase in sodium amount when ris- increase in comparison with the reference composition (prepared
ing the dregs incorporation in the formulations, still no microstruc- without using dregs as fine filler): 25% (10 wt% dregs), 39% (15
tural modification were observed (e.g. sodium salts formation). wt% dregs), 37% (20 wt% dregs) and 71% (25 wt% dregs). The com-
This result is of crucial importance demonstrating that the dregs position containing 20 wt% dregs is an exception to this general
do not negatively affect the geopolymer microstructure and that trend, since its tensile strength is slightly inferior to that observed
stable geopolymerization products were formed. for the composition containing 15 wt% dregs. Nevertheless, the
higher standard deviation of the latter (15 wt% dregs) suggests
3.2.4. Mechanical resistance, density and water absorption of similar tensile strength for both compositions. The apparent den-
hardened bodies sity followed a similar trend, still differences between the compo-
Fig. 9 presents the tensile strength and the apparent density of sitions were less relevant.
the mortars (1 day cured) with and without dregs as fine filler. As Fig. 10 shows that the compressive strength of the specimens
was generally enhanced when the dregs concentration in the mor-
tars increased, reaching the maximum value (21 MPa) with for
the 25 wt% dregs-containing mortar. This value corresponds to an
increase of around 34% in comparison with the reference mortar.
ANOVA confirms the statistical significance of variations (p-value
<0.05, Table 3). Considering that the calorimetric results have sug-
gested that the dregs are not reactive or exhibit low reactivity the
observed resistance gain is most probably due to their filler effect.
In fact, their fine particle size improves the mixture compactness.
In line with this remark the water absorption (shown in Fig. 10)
drops significantly (up to 20%) as the dregs amount rises, clearly
demonstrating a decrease in mortars’ porosity. Once again ANOVA
validates the significance of these results (p-value <0.05). Despite
the decrease in water absorption the optical micrographs shown
in Fig. 11 did not show significant differences in microstructure
and macro porosity, suggesting that the eventual differences in
pore size and volume are below the detection limit of this
Fig. 5. Influence of the dregs incorporation content on the temperature evolution of
technique.
geopolymeric slurries upon curing.
 R.M. Novais et al. / Construction and Building Materials 184 (2018) 464–472 469

Fig. 7. Photograph of the geopolymer mortars containing distinct dregs incorporation content. From left to right: 25 wt%, 20 wt%, 15 wt%, 10 wt% and 0 wt%.

Fig. 8. SEM micrographs and EDS spectrum of dreg-containing geopolymer mortars: a) 0 wt%, b) 15 wt% and c) 25 wt% dregs.
470 R.M. Novais et al. / Construction and Building Materials 184 (2018) 464–472

reference mortar. The correlation coefficient was also included in

the figure, being higher than 0.99 for all the specimens. Within
the first 90 min the differences between the mortars containing
various dregs amounts are minor, in line with the water absorption
data presented in Fig. 10. As the adsorption time increases differ-
ences between the reference and the dregs-containing mortars
are intensified: the reference mortar showing systematically
higher absorption rate and water absorption than the dregs-
containing mortars, suggesting differences not only in the samples
total porosity but also in their pore size distribution. Once again
the differences between the specimens containing various dregs
contents are minor, the exception being the composition contain-
ing 20 wt% dregs which shows higher water absorption than their
dregs-containing counterparts. The reason for this higher absorp-
Fig. 9. Tensile strength and apparent density of the mortars cured for 1 day.
tion was attributed to the higher heterogeneity of this specimen
(see Fig. 10). Anyway these results validate the decrease in porosity
and the corresponding increase of specimen’s mechanical perfor-
mance when dregs are added to the compositions as fine filler.
Fig. 10 also shows a light progression of compressive strength
from 7 to 28 days curing for the reference and the higher contain-
ing dregs (25 wt%) mortars, suggesting that the most relevant
geopolymerization reactions occur in the first days, giving rise to
stable products. The compositions containing between 10 and 20
wt% dregs showed the opposite behavior (decrease in compressive
strength with time). Nevertheless, the mechanical performance
drop was negligible for the compositions containing 10 and 15
wt% dregs, being relevant for the composition containing 20 wt%
dregs. Not surprisingly, this composition (20 wt% dregs) also
exhibited the highest standard deviation at the 28th day, suggest-
ing that this performance decay is associated with the limited
number of tested specimens (three) and not to any durability
issues. In fact, the latter was clearly demonstrated by the increase
Fig. 10. Compressive strength and water absorption of the mortars cured for 7 and in compressive strength with curing observed for the higher con-
28 days. taining (25 wt%) dregs mortar.
The maximum compressive strength here achieved (21 MPa)
To fully characterize the pore size distribution of the mortars for the geopolymer mortars are inferior to other literature values
capillary water absorption tests were performed and results are [26–28]. However, the focus of the present investigation was on
presented in Fig. 12. Fig. 12b shows that the reference mortar the simultaneous use of two unexplored wastes coming from the
has the highest capillary index, while the dregs-containing mortars paper and pulp production (FA and dregs) and not on the ultimate
exhibit significantly lower index, between 10.5 and 14.7%, than the mechanical performance. Indeed, the wastes were used as-received

Fig. 11. a) View of the specimens (2  2  4 mm3) used for optical characterization, and the corresponding optical micrographs of mortars containing distinct amounts of
dregs: b) 0 wt%, c) 10 wt% d) 15 wt%, e) 20 wt% and f) 25 wt%.
 R.M. Novais et al. / Construction and Building Materials 184 (2018) 464–472 471

Fig. 12. a) Capillary water absorption of mortars prepared with and without using dregs as fine filler and b) corresponding capillary index.

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